CN104254504B - The geopolymer formulation and method of dimensionally stable - Google Patents

Abstract

The invention discloses a kind of method for being used to prepare the geo-polymer splicing adhesive composition for cementitious product, the cementitious product is such as concrete, pre-cast building element and panel, mortar, for the patching material of road repair and other patching materials.The geo-polymer cementitious composition of some embodiments is made by mixing the aluminosilicate mineral material through thermal activation, calcium sulphoaluminate cement, calcium sulfate and the Synergistic mixtures of chemical activating agent and water.

Description

The geopolymer formulation and method of dimensionally stable

Technical field

The present invention relates generally to available for the cementitious composition containing alumino-silicate base geological polymer in a variety of applications. Especially, the present invention relates generally to this cementitious composition, it is provided with regard to setting time, heat release dimensional stability, consolidating of reducing Property needed for for overall material shrinks during change, and other this required properties.

Background technology

Ko United States Patent (USP) No.6,572,698 disclose a kind of activated alumino-silicate binding agent, and it contains aluminosilicate Salt, calcium sulfate and the activator containing alkali metal salt.The alumino-silicate is selected from blast furnace slag, clay, plaster and industry pair Product (such as flying dust), and with the Al more than 5 weight %₂O₃Content.Blast furnace slag exists with the amount less than 35 weight %, and It is added to the cement kiln dust (CKD) of 1 to 20 weight % amount as activator in mixture.

Galer et al. United States Patent (USP) No.4,488,909 discuss comprising Portland cement, alumina cement, calcium sulfate and The cementitious composition of lime.The cementitious composition includes Portland cement, alumina cement, calcium sulfate and lime.Such as flying dust Volcanic ash, montmorillonitic clay, diatomite and float stone can amount to of about 25%.The cementitious composition includes about 14 to 21wt% Alumina cement.

Perez-Pena et al. United States Patent (USP) No.6,869,474 is discussed for preparing cement base products (such as cement Plate) cementitious composition.This is realized in the following way：Alkanolamine is added to the hydraulic cement of such as Portland cement, And form slurry with water under conditions of the initial slurry temperature of at least 90 °F (32 DEG C) is provided.It may include other reactive material Material, such as alumina cement, calcium sulfate and pozzolanic material (such as flying dust).

Perez-Pena et al. United States Patent (USP) No.7,670,427 is discussed for preparing cement base products (such as cement Plate) the cementitious composition with early stage compressive strength solidification extremely fast, it is obtained in the following way：By alkanolamine and Phosphate is added in hydraulic cement (such as Portland cement), and is providing the initial slurry temperature of at least 90 °F (32 DEG C) Under the conditions of with water formed slurry.It may include other reactive explosive, as alumina cement, calcium sulfate and pozzolanic material are (like flying Ash).

Perez-Pena U.S. published patent application No.US2010-0071597A1 is disclosed using flying dust and citric acid Alkali metal salt (such as sodium citrate) form the formula of concrete mix.The at most 25wt% hydraulicity of formula can be used Cement and gypsum, although their use is not preferable.The activated flying dust binding agent described in this application can with Interacted in pressing from both sides aeriferous conventional foaming system, and thus prepare thistle board.

Brook et al. United States Patent (USP) No.5,536,310 disclose a kind of cementitious composition, and it contains 10-30 parts by weight (pbw) hydraulic cement (such as Portland cement), 50-80pbw flying dust, and 0.5-8.0pbw as free acid represent Carboxylic acid (such as citric acid) or its alkali metal salt (such as citric acid tri potassium or trisodium citrate), and other conventional additives (bags Retardance agent addition agent is included, such as boric acid or borax).

Dubey United States Patent (USP) No.6,641,658 disclose a kind of Portland cement base cementitious composition, and it contains 35- 90% Portland cement, 0-55% volcanic ash, 5-15% alumina cement and 1 to 8% insoluble anhydrous gypsum form Calcium sulfate, although having used the volcanic ash (such as flying dust) of a large amount, the calcium sulfate generation of the insoluble anhydrous gypsum form For soluble conventional gypsum powder/gypsum, discharge to increase heat and reduce setting time.The cementitious composition can include lightweight Gather materials and filler, superplasticizer and additive (such as the sodium citrate as reaction retarding agent).

Nakashima et al. United States Patent (USP) No.7618490B2 discloses a kind of spray material, its include calcium sulphoaluminate, One or more in ca aluminosilicate, calcium hydroxide, Fluorine source and portland cement concrete.Calcium sulfate can be used as anhydrous gypsum or Added as semi-hydrated gypsum.

Nakano et al. United States Patent (USP) No.4655979 discloses a kind of using calcium silicates base cement, alkali metal retardance Agent, calcium sulphoaluminate (CSA) cement and the optional calcium sulfate in concrete composition is may be added to that to prepare celluar concrete Method.

Godfrey et al. U.S. published application No.2008/0134943A1 discloses a kind of waste by forming as follows Encapsulating material：At least one aluminium sulfate and calcium sulfate of alkaline-earth metal, and optional inorganic filler (such as blast furnace slag, Fine-ground fly-ash, fine silicon dioxide, limestone), and organic and inorganic fluidizing reagent.Preferably, at least one of alkaline-earth metal Aluminium sulfate includes calcium sulphoaluminate (CSA).A kind of at least one sulphur aluminic acid that suitably composition can be for example comprising alkaline-earth metal Salt and gypsum and fine-ground fly-ash (PFA), wherein about the 86% of gypsum particle have the granularity less than 76um, and PFA particles About 88% have below 45um granularity.One example includes 75% (70: 30CSA: CaSO4.2H2O)；25% pulverized powder Coal ash；Water/solid ratio is 0.65.

Li et al. United States Patent (USP) No.6730162 discloses double cementitious compositions, and it includes the first hydraulic-composition, First hydraulic-composition has 2.5% to 95wt.% C₄A₃(it is chemical symbol to S, wherein C=CaO, S=SiO₂, A=Al₂O₃) (in other words calcium sulphoaluminate) and 2.5 to 95wt.% calcium sulfate semihydrate and/or anhydrous gypsum.Sulphur aluminic acid Salt cement or ferrous aluminate cement are to contain C₄A₃The example of S cement.It can also include and be added selected from following mineral filler Agent：Slag, flying dust, volcanic ash, silica soot, lime stone fines, lime industrial by-products and waste material.

Deng et al. Chinese published application CN101921548A discloses a kind of by following obtained sulphate aluminium cement Composition：90-95wt% sulfoaluminate clinker and anhydrous gypsum, quartz sand, the flying dust from waste incineration, hydroxypropyl first Base cellulose ether, redispersible rubber powder and fiber.The sulfoaluminate clinker and anhydrous gypsum meet sulphate aluminium cement Standard, i.e. GB20472-2006.

Jung et al. South Korea published application No.KR 549958B1 disclose a kind of aluminium cement, CSA, gypsum, citric acid The composition of calcium and hydroxycarboxylic acid.

Noh South Korea published application No.KR2009085451A discloses a kind of powdered blast furnace slag, gypsum and CSA Composition.The gypsum can have 4 microns or smaller of particle mean size.

South Korea published application No.KR2009025683A disclose by grind cement, anhydrous gypsum, SiO 2 powder, Waterproof powder, flying dust, calcium sulphoaluminate type expanding material and inorganic binder and the powder-type for being used for concrete and mortar obtained Waterproof material.

Gyu et al. South Korea published application No.KR2010129104A discloses the composition for gunite concrete to be blended Include (in terms of wt.%)：Metakaolin (5-20), calcium sulphoaluminate (5-20), anhydrous gypsum (20-45) and flying dust (30-50).

The adhesive material of the dimensionally stable containing geopolymer formulation is needed, it provides to reduce after solidification and received Contracting, improved initial and final temperature behavior, controlled and/or optimization setting time, improved intensity and be advantageous to this material Material is in building construction, shaping cementitious product and other application (such as cementing structure, cementing structure element and molding cementitious product) In other properties used, and need the method for preparing this material and forming this structure, element and product.

The content of the invention

The invention provides improved geo-polymer cementitious composition and the method for preparing this composition, it has It is at least one, and more than one property being highly desirable in many cases, such as significantly change with after solidification in the curing process The dimensional stability entered；Improved and adjustable initial and final setting time；The working time of extension；In mixing, solidification Produced with the temperature changed in solidification process；And other improved properties as described herein.In many of this embodiment (if not all) in, there is provided improved property is without significantly loss early stage compressive strength, final (if any) Compressive strength or other intensity properties.In fact, some embodiments provide unexpected early stage compressive strength and most final pressure The increase of contracting intensity.

The improved property of those of the present invention and other embodiment is provided compared to previous geo-polymer binding agent (such as flying dust based binder) and containing notable geology polymer content other be glued binding agents obvious advantage.At some In preferred embodiment, geo-polymer cementitious composition of the invention is by least one or more of water and drying or powder type The solution or slurry of cementation reaction component are formed.The geology through thermal activation that the cementation reaction component includes effective dose is gathered Compound alumino-silicate materials (such as flying dust)；Calcium sulphoaluminate cement；And calcium sulfate.Also can be by one or more alkali metal chemical activations Agent (alkali metal salt or alkali metal base of such as citric acid) is added in solution, or is added to reactive powder in a dry form, Or it is added to slurry as liquid additive.Optionally, the slurry or solution can mix other additives (such as water reducer, Coagulation accelerator or retarding agent, air entraining agent, foaming agent, wetting agent, lightweight or other gather materials, reinforcing material, or other additives) To provide or change the property of slurry and final products.

In many preferred compositions of the present invention, dry or the cementation reaction component of powder type includes about 65 to about The 97 weight % aluminosilicate mineral material (such as flying dust) through thermal activation, about 2 to about 30 weight % calcium sulphoaluminate cement, peace treaty 0.2 to about 15 weight % calcium sulfate, with the overall dry weight of whole cementation reaction components.In the preferred composition of the present invention In, the cementation reaction component includes the calcium sulphoaluminate cement of about 1 to about 200 parts by weight, with 100 parts by weight through thermal activation Aluminosilicate mineral material meter.Dry weight has the definition generally approved, i.e. in terms of not aqueous.

In other embodiments, calcium sulphoaluminate cement and the blending of aluminous cement of two or more types can be used Thing, and the amount and type of calcium sulphoaluminate cement and aluminous cement may depend on they chemical composition and granularity (Blaine is thin Degree) and change.In this embodiment and other embodiment, the Blaine fineness of calcium sulphoaluminate cement is preferably greater than about 3000, More preferably greater than about 4000, even more preferably greater than 5000, most preferably greater than about 6000.

In some preferred embodiments, the amount of alkali metal chemical activating agent be about 0.5 weight % to about 10 weight %, with institute State the overall dry weight of cementation reaction material.It is highly preferred that the scope of alkali metal chemical activating agent is about 1% to about 6%, preferably About 1.25% to about 4%, more preferably from about 1.5% to about 3.5%, most preferably from about 1.5% to about 2.5%, with the cementation reaction The gross weight meter of property material.Sodium citrate and potassium citrate are preferable alkali metal acid activators, although citric acid can also be used The blend of sodium and potassium citrate.Needs depending on application and the application, it is possible to use alkali metal base, such as alkali metal hydroxide Thing and alkali silicate.

Different from previous flying dust geopolymer formulation, these and other preferred embodiments of the invention are established as carrying For geo-polymer cementitious composition, the geo-polymer cementitious composition dimensionally stable, and resist unrestricted and limited Under the conditions of solidification and hardening when cracking.For example, the short-term free shrink of some preferred embodiments of the present invention is typically smaller than About 0.3%, preferably less than about 0.2%, more preferably less than about 0.1%, most preferably less than about 0.05% (after initial solidification simultaneously Measured in 1 to 4 hour of mixing).In this preferred embodiment, the long-term contraction of composition is also usual in the curing process Less than about 0.3%, more preferably less than about 0.2%, most preferably less than about 0.1%.

For in those embodiments about dimensional stability and the other control shunk, the amount of calcium sulphoaluminate cement with Aluminosilicate mineral material of 100 parts by weight through thermal activation is calculated as about 2.5 to about 100 parts by weight, more preferably with 100 parts by weight through heat The aluminosilicate mineral material of activation is calculated as about 2.5 to about 50 parts by weight, most preferably with alumino-silicate of 100 parts by weight through thermal activation Mineral matter is calculated as about 5 to about 30 parts by weight.There is weight for the control wherein to the dimensional stability represented by Material shrinkage The embodiment for the property wanted, (the aluminosilicate mineral material i.e. through thermal activation is (like flying with cementation reaction material for the amount of alkali metal activator Ash), calcium sulphoaluminate cement and calcium sulfate) overall dry weight be even more preferably about 1 to about 3%, even more preferably with cementation reaction The overall dry weight of material is about 1.25% to about 2.75%, most preferably using the overall dry weight of cementation reaction material as about 1.5% To about 2.5%.

Compared to previous geo-polymer cementitious product, the geology of the dimensionally stable of the preferred embodiments of the present invention polymerize Compositions also show the unexpected reduction of maximum temperature rise in the solidification process of composition.Because the reason and correlation are former Cause, the resistance thermal cracking of these embodiments reach unexpected degree.For example, in some preferred embodiments, temperature rise is generally small In about 50 °F (28 DEG C), more preferably less than about 40 °F (22 DEG C), most preferably less than about 30 °F (17 DEG C).

These and other preferred embodiments of the present invention also show that the increased speed of unexpected early strength.Example Such as, in some this embodiments, their 4 hours compressive strengths can be more than about 1000psi (6.9MPa), preferably greater than about 1500psi (10.3MPa), most preferably more than about 2500psi (17.2MPa).In such an embodiment, their 24 hours are compressed Intensity increase can be more than about 1500psi (10.3MPa), more preferably above about 2500psi (17.2MPa), most preferably more than about 3500psi(24.1MPa).In those and other embodiment, their 28 days compressive strengths can also be more than about 3500psi (24.1MPa), more preferably above about 4500psi (31.0MPa), most preferably more than about 5500psi (37.9MPa).In other realities Apply in example, the composition can be increased to compressive strength about by about 500psi (3.5MPa) after 1 to 4 hour 4000psi (27.6MPa), more preferably compressive strength can be increased to about 5000psi (10.3 by about 1500 at 24 hours later To 34.5MPa), most preferably after 28 days can by compressive strength by about 3500 increase to about 10000psi (24.1 to 69MPa).In addition, some geo-polymer cementitious compositions in the preferred embodiments of the present invention also have in wet conditions Fabulous durability, and final Wet Compression intensity is similar to dry compressive strength.For example, in certain embodiments, their 28 days Water saturation compressive strength can generally be more than about 3500psi (24.1MPa), more preferably above about 4500psi (31.0MPa), optimal Choosing is more than about 5500psi (37.9MPa).

Due to the geo-polymer and the calcium sulphoaluminate cement of combination that are activated through alkali metal and calcium sulfate by slurry to solid The setting time of state is generally relatively short, it is therefore contemplated that combines the preferred embodiment of all these components also by with short solidification Time and limited working time.Unexpectedly, however, the setting time provided by the preferred embodiments of the present invention is not limited to In short setting time (typically smaller than 15 minutes), and the obvious control to slurry Hirschfeld-Klinger reaction is there is provided, so as to allow to starch Material solidification and the notable extension of working time.

For example, in certain embodiments, composition can be formulated as having short setting time, such as less than about 10 minutes. In other preferred embodiments, composition can be formulated as the solidification with the extension between about 10 to about 30 minutes.It is more excellent at other In the embodiment of choosing, composite formula is preferably chosen as providing the setting time of about 30 to about 60 minutes.It is most preferred at other In embodiment, composition can be formulated as having it is long of about 60 to about 120 minutes, about 120 to about 240 minutes or the longer time (such as Fruit need if) setting time.

In addition, may be selected and (if desired) extends the setting time of this embodiment, without significantly (if Words) loss resistance to retractable property, compressive strength and other intensity properties.As a result, this embodiment unexpectedly can be used for In following application：Due to the solidification and the working time that need to extend without unacceptable contraction or loss of strength, thus can not Using previous geo-polymer base product and with geo-polymer component cementitious product.

In some preferred embodiments, the extraordinary stretch-bonded that composition of the invention is also produced with the base material of lower section is strong Degree.For example, the preferred tensile bond strength between the composition and concrete substrate of this embodiment is preferably greater than about 200psi (1.4MPa), most preferably more than about 300psi (2.1MPa).In certain embodiments, have compared to usual more than 12, it is more logical Often greater than 13 surface p H Portland cement sill and product, the dimensionally stable of the invention through being fully cured and hardening The surface p H of geo-polymer cementitious composition is also improved.In some preferred embodiments, this composition is in installation Measure within 16 hours afterwards, and preferably have less than about 11, more preferably less than about 10.5, most preferably less than about 10 pH.With regard to this For, use ASTM F-710 (2011) testing standard measurement surface pH.

In many preferred embodiments, geo-polymer cementitious composition of the invention does not need calcium silicates base hydraulicity water Mud (such as Portland cement) is used for intensity increase and dimensional stability.In other embodiments, Portland cement can be mixed to carry For specific required property.Unexpectedly, however find, depending on the concrete composition of embodiment, excessive Portland cement Actually in the curing process with reduce the dimensional stability of composition after solidification, and the dimensionally stable of non-increasing composition Property.

The preferred embodiments of the present invention for mixing calcium silicates base hydraulicity cement, the limitation to this hydraulic cement It may depend on the concrete composition of embodiment and change, but the phase relative to the calcium silicates hydraulic cement with reduction amount can be passed through Determined with the contraction increase of the contraction of embodiment.This embodiment it is some in, Portland cement content is not to be exceeded instead About 15 weight % of the weight of answering property powdery components, in another preferred embodiment, reactive powdery components are not to be exceeded in it 10 weight % of weight, in a further preferred embodiment, about 5 weight % of the weight of reactive powdery components are not to be exceeded in it, In a further preferred embodiment, the Portland cement of real mass is not present in reactive powdery components.

In certain embodiments also it has been unexpectedly found that excessive calcium sulphoaluminate cement can cause dimensional stability Loss, as shown in the contraction increase after the initial solidification of composition.For need significance degree dimensional stability and/ Or application of the control to prevent crack arrest, leafing and other failure modes is shunk, the amount of calcium sulphoaluminate cement is with 100 dry weight parts Aluminosilicate mineral material meter through thermal activation is preferably from about 10 to about 40 dry weight parts.

In other preferred embodiments, also unexpectedly find, it is proportional to the calcium sulphoaluminate cement in composition The amount of existing calcium sulfate can reduce the potential unfavorable effect caused by calcium sulphoaluminate cement content, such as shrink.This In embodiment, the amount of calcium sulfate is preferably from about 2 to about 200 parts by weight in terms of 100 parts by weight calcium sulphoaluminate cement.

Material shrinkage for most effectively controlling those embodiments, the amount of calcium sulfate is with 100 dry weight part calcium sulphoaluminates Cement is calculated as about 10 to about 100 dry weight parts, is more preferably calculated as about 15 to about 75 dry weights with 100 dry weight part calcium sulphoaluminate cement Part is measured, is most preferably calculated as about 20 to about 50 dry weight parts with 100 dry weight part calcium sulphoaluminate cement.Early stage compressive strength wherein Increase with importance embodiment in, the preferred amounts of the amount of calcium sulfate are calculated as about with 100 dry weight part calcium sulphoaluminate cement 10 to about 50 parts.

In other embodiments of the invention, added to type (predominantly dihydrate, half of the calcium sulfate in composition Hydrate or anhydrous gypsum) to the early stage compressive strength through partially cured composition increase (when i.e. less than about 24 hours) tool Have a significant impact.Unexpectedly, it has been found that main each embodiment using calcium sulfate anhydrite uses compared to main The embodiment of dihydrate form has bigger early stage compressive strength, and in certain embodiments, can have with mainly making With the comparable early stage compressive strength of those embodiments of calcium sulfate hemihydrate.In other embodiments, two or more Sulfuric acid calcium type (dihydrate, semihydrate or anhydrous gypsum) can use together, and adjust different types of amount to provide Improvement to the compressive strength of composition controls.Similarly, the calcium sulfate of different type and amount can be used alone or in combination, to adjust Save required contraction and other properties of composition.

When shrinkage is mainly considers, other embodiment of the invention incorporation particle mean size is preferably from about 1 to about 100 Micron, about 1 to about 50 micron, about 1 to about 20 micron of calcium sulfate.These embodiments provide the unexpected of anti-contracility Improve, in other embodiments, can be provided in the calcium sulfate granularity at least in preferred scope in the solidification process in composition pair The increased significant contribution for improving speed of intensity.

In other embodiments, it was unexpectedly found that, although substantially water-insoluble dead plaster (anhydrous stone Cream) there is low water solubility and (if any) reactivity limited in the composition assumed before, but it can provide weight The benefit wanted.For example, unexpectedly finding, anhydrous gypsum is by reducing in those and the solidification process of other embodiment Shrink, so as to provide compared to the significantly improved dimensional stability control of prior art compositions.Anhydrous gypsum is also provided and compared In prior art compositions significantly improved early stage and long compressive intensity, and in some cases, there is provided with using calcium sulfate Semihydrate or dihydrate are as the composition of calcium sulfate source is comparable or more preferable early stage and long compressive intensity.Specific In embodiment the selection of the type of calcium sulfate used by depending on early strength it is increased needed for speed and other properties Balance (setting time and anti-contracility as being used for specific final application).

In other embodiments, the granularity of calcium sulfate and form provide (it is small to be less than about 24 to the early strength of composition When) increased notable and unexpected influence.In such an embodiment, the use of the calcium sulfate of relatively small granularity provides The faster increase of early stage compressive strength.In those embodiments, the preferred average particle size of calcium sulfate is about 1 to 100 micro- Rice, most preferably from about more preferably from about 1 to 50 micron, 1 to 20 micron.

In certain embodiments, the composition also shows Self-leveling behavior after initial mixing, and provides simultaneously One or more of foregoing unexpected performance characteristics.It can be used in terms of the Self-leveling of material in a variety of situations and application, Manufacture such as the Self-leveling end liner on floor, concrete top, accurate concrete product and panel, starched in the Constracture unit strongly enhanced Setting of material etc..The composition of those embodiments is Self-leveling after initial mixing, the reactivity of its reclaimed water and the present invention The weight ratio of powder is about 0.15 to about 0.4, more preferably 0.17 to 0.35, even more preferably from 0.20 to 0.30.Or in other realities Apply in example, composition can also be with the shapable thick pasty consistency offer after initial mixing, and similarly provides one simultaneously Individual or multiple improvement performance characteristics.

For flying dust of the optimization formula of Self-leveling and repairing composition comprising about 65 to about 95 weight %, about 2 to about 30 Weight % calcium sulphoaluminate cement, and about 0.2 to about 15 weight % calcium sulfate.In certain embodiments, geology of the invention Polymer cementitious composition can be sprawled on substrate surface, and wherein geo-polymer is glued binding agent and mixed as gravity flow flat products Close, and be poured into about 0.02cm to about 7.5cm effective thickness.

The physical characteristic offer of this product is suitable for those embodiments of business, industry and other high traffic fields The good example of benefit, i.e. dimensional stability, and the resistance of physics crisis (physical distress) mobile to size, and To the high surface resistive for wearing away and wearing.Depending on application, the substrate surface being time-consuming and expensive penetrate measure (such as shot-peening, scribing, Water spray, scab are milled) it can be minimized or avoid completely.

In other aspects of the present invention, preferred embodiment provides the side of the cementitious composition for preparing dimensionally stable Method, the cementitious composition of the dimensionally stable have the setting time for being adapted to concrete application, the increase of good early strength and Final compressive strength and other strength characteristicies, improved surface p H, improved and the tensile bond strength of base material and other benefits. In some preferred embodiments, those methods comprise the following steps：The alumino-silicate through thermal activation is prepared (to be preferred from C classes to fly Ash), calcium sulphoaluminate cement, the unexpected effective Synergistic mixtures of calcium sulfate and alkali metal chemical activating agent.

In some preferred embodiments of this method, preferred mixture is prepared using the component of such as those described above, with The cementation reaction powder for including the C classes flying dust through thermal activation, calcium sulphoaluminate cement and calcium sulfate is formed, the calcium sulfate is selected from Calcium sulfate dihydrate, calcium sulfate hemihydrate, dead plaster and their mixture (are preferably that granularity is micro- less than about 300 The fine particulate form of rice).

In those embodiments, it will further dry or the chemical activating agent of liquid form be added in mixture, it is described Chemical activating agent includes the alkali metal salt for being preferably selected from the alkali metal salt of organic acid, alkali metal hydroxide and alkali silicate Or alkali metal base.In a subsequent step, water and optional superplasticizer (particularly Carboxylation plasticizer materials) are added, with Form the stable slurry mixture that can be used in the application suitable for geo-polymer cementitious product.

In a preferred method, mixture is under about 0 DEG C to about 50 DEG C of initial temperature, more preferably from about 5 DEG C to about 40 DEG C Under initial temperature, under even more preferably about 10 DEG C to about 35 DEG C of initial temperature, it is made under most preferably from about 25 DEG C of environment temperature. In such an embodiment, first minute after cementation reaction powder, activator and water are present in mixture first During measure master mix initial temperature.Certainly, the temperature of master mix can become during described first minute Change, but in this preferred embodiment, the temperature of slurry is preferably remained in listed scope.

In some preferred embodiments, relatively low energy hybrid can be used in slurry, and still obtains simultaneously good mixed The composition of conjunction.In some in this method for optimizing, using with by low speed hand drill blender or with about 250RPM or more The energy that those energy of the equivalent blender offer of big rated value are suitable carrys out mixed slurry.Therefore, although using relatively few The water (water is used to prepare the slurry for being used for forming final composition) of amount, the geo-polymer combination of this preferred embodiment Thing is still easily mixed.

In many examples, other additives of not considered cementation reaction powder can be mixed to slurry and total In body geo-polymer cementitious composition.Other this additives such as water reducer (such as above-mentioned superplasticizer), coagulation accelerator, It is redispersible poly- to solidify retarding agent, air entraining agent, foaming agent, wetting agent, shrinkage control agent, viscosity modifier (thickener), film forming Compound powder, film forming polymer dispersion, colouring agent, corrosion control agent, reduce alkali-silicon dioxde reaction adulterating agent, discrete Reinforcing fiber, and internal curing agent.Other additives may include filler, as sand and/or other gather materials, light filler, volcano One or more in grey mineral matter, mineral filler etc..

Although as above separately discussing, the preferred geopolymer formulation of the present invention is compared with each in mixture There is at least one above-mentioned particular advantages (and further begging for according to this paper in prior art geo-polymer cementitious composition By, example and data it is obvious those), and can have above-mentioned particular advantages (and according to this paper it is discussed further, Example and data and it is obvious those) in the combination of two or more.

The flying dust geology polymerization that many (if simultaneously not most) in embodiments of the invention utilizes for continuity of environment Thing, it includes postindustrial waste material as primary raw material source.This significantly reduces the life cycle carbon emission of obtained product and Life cycle includes energy.

The geo-polymer cementitious composition of the preferred embodiments of the present invention can be in place of using other adhesive materials, especially Be wherein solidification and working time flexibility, dimensional stability, compressive strength and/or other intensity properties it is important or it is required should With middle use.For example, in the application of various concrete products, including structural concrete panel for floor, slab and wall, use In the wall and floor underlayments, highway of installation floor finishing material (such as Ceramic Tiles, natural stone, vinyl brick, VCT and carpet) Top layer and bridge maintaining, pavement and other terraces, outside plaster and stucco, Self-leveling top and the end liner that binds, it is used for The whitewashing of native stone in firm ground, hill-side and mine and gunite concrete, for fill peaceful slip seam, hole and other not Repairing maintenance mortar, the statue and wall ornamentation for inside and outside application of flat surface, and for repairing road and floorings In pit patching material.

Other examples are included for precast concrete product and the building products with excellent moisture durability is (as being glued Plate, masonry block, brick and paveio(u)r) purposes.In some applications, this pre-cast concrete products (such as cement plate) preferably exist It is made under the conditions of following：The condition, which provides, to be suitable to be poured into fixed or mobile mould or be cast in coagulating on continuous moving band Gu the time.

The geopolymer formulation of some embodiments of the present invention can be used together from different fillers with additive, described Different fillers and additive include adding air with special ratios (including pre-cast building element, to be built with preparing lightweight cementitious product Build repair products, there is good swelling properties and shrinkage-free repairing composition (such as suitable for road repair and road surface)) Foaming agent and air entraining agent.

Other advantages, benefit and the aspect of each embodiment of the present invention are discussed below, are shown in appended accompanying drawing, and root It is readily appreciated by one skilled in the art according to disclosing in more detail below.Unless otherwise noted, otherwise this paper all percentages, ratio Rate and ratio are by weight.

Brief description of the drawings

Figure 1A is the figure of the contraction time result of comparative example 1.

Figure 1B is the photo of the slump of example 1.

Fig. 2A is the photo of the slump of comparative example 2.

Fig. 3 A are the photo of the slump of comparative example 3.

Fig. 3 B are the figure of the contraction time result of comparative example 3.

Fig. 4 A are the initial flow behavior of the composition in example 4 and the photo to collapse for mixture 1 and 2.

Fig. 4 B are the initial flow behavior of the composition in example 4 and the photo to collapse for mixture 3.

Fig. 4 C are the initial flow behavior of the composition in example 4 and the photo to collapse for mixture 4.

Fig. 4 D are photo-mixture 1,2-1 and 2-2,3-1 and the 3-2 and 4-1 and 4-2 for the composition studied in example 4 All rod (from left to right) crackings in a mold.

Fig. 5 A are the photo of the mixture 1-2 (from left to right) and 3-4 (from left to right) of example 5 slump cake.

Fig. 5 B are the initial flow of example 5 and the block diagram of slump result.

Fig. 5 C are the figure of the slurry temperature rise result of example 5.

Fig. 6 A are the figure of the contraction time of example 6.

Fig. 6 B are the figure of the slurry temperature rise of the composition of the invention in example 6.

Fig. 7 A are the photo of the slump cake of the mixture 1 of the composition of example 7.

Fig. 7 B are the photo of the slump cake of the mixture 2,3 and 4 of the composition of example 7.

Fig. 7 C are the figure of the contraction of the composition of the invention in example 7.

Fig. 7 D are the figure of the slurry temperature rise of the composition of the invention of example 7.

Fig. 8 A are the figure of the contraction of the composition of the invention in example 8.

Fig. 8 B are the figure of the slurry temperature rise of the composition of the invention of example 8.

Fig. 9 A are the figure of the contraction of the composition of the invention in example 9.

Fig. 9 B are the figure of the slurry temperature rise of the composition of the result of the present invention of example 9.

Figure 10 A are the figure of the contraction of the composition of the invention in example 10.

Figure 10 B are the figure of the slurry temperature rise of the composition of the result of the invention of example 10.

Figure 11 A show the photo of the slump cake of the composition of example 11.

Figure 11 B are the figure of the contraction of the composition of the invention in example 11.

Figure 11 C are the figure of the slurry temperature rise of the composition of the invention of example 11.

Figure 12 A are the figure of the contraction of the composition of the invention in example 12.

Figure 12 B are the figure of the slurry temperature rise of the composition of the result of the invention of example 12.

Figure 13 A are the photo of the slump cake of the composition of the invention of example 13.

Figure 13 B are the figure of the contraction of the composition of the invention in example 13.

Figure 13 C are the figure of the slurry temperature rise of the composition of the invention of example 13.

Figure 14 A are the figure of the contraction of the composition of the invention in example 14.

Figure 15 A are the figure of the contraction of the composition of the invention in example 15.

Figure 15 B are the figure of the slurry temperature rise of the composition of the invention of example 15.

Figure 16 A contain the photo of the slump cake of the composition of the invention of example 16.

Figure 16 B are the figure of the contraction of the composition of the invention in example 16.

Figure 17 A contain the photo of the slump cake of the composition of the invention of example 17.

Figure 17 B are the figure of the contraction of the composition of the invention in example 17.

Figure 17 C are the figure of the slurry temperature rise of the composition of the invention of example 17.

Figure 18 A are the figure of the contraction of the composition of the invention in example 18.

Figure 18 B are the figure of the slurry temperature rise of the composition of the invention of example 18.

Figure 19 A are the figure of the contraction of the composition of the invention in example 13.

Figure 19 B are the figure of the slurry temperature rise of the composition of the invention of example 19.

Figure 20 A are the figure of the contraction of the composition of the invention in example 20.

Figure 20 B are the figure of the slurry temperature rise of the composition of the invention of example 20.

Figure 21 A are the figure of the contraction of the composition of the invention in example 21.

Figure 21 B are the photo of the mixture Isosorbide-5-Nitrae hour contraction rod for example 21.

Figure 21 C are the figure (contraction started at 1 hour of the pole early stage Material shrinkage of the composition of the invention of example 21 Test).

Figure 21 D are the figure of the slurry temperature rise of the composition of the invention of example 21.

Figure 22 A are the figure of the contraction of the composition of the invention in example 22.

Figure 22 B are the figure of the slurry temperature rise of the composition of the invention of example 22.

Figure 23 is figure (the contraction survey started at 1 hour of the pole early-age shrinkage of the composition of the invention of example 23 Examination).

Figure 24 is the figure of the contraction of the composition of the invention in example 27.

Figure 25 includes the photo of the casting cube (in brass cube mold) for the composition studied in example 28.

Figure 26 is the figure of the contraction of the composition of the invention in example 29.

Figure 27 A are the figure of the contraction of the composition of the invention in example 30.

Figure 27 B are the figure of heat release and the slurry temperature rise behavior of the composition in example 30.

Figure 28 A are the heat release and slurry temperature rise behavior of the lightweight compositions of some embodiments of the present invention in example 31 Figure.

Embodiment

Table A shows the group of the geo-polymer cementitious composition of the dimensionally stable of some currently preferred embodiments of the present invention Into it is represented with the parts by weight (pbw) of independent or aggregation component.

Table A shows the geo-polymer cementitious composition of the dimensionally stable of this preferred embodiment of the present invention by two kinds Component forms：Reactive powdery components A (also referred to as " cementation reaction material ", its be defined as the purposes of the present invention through The alumino-silicate of thermal activation, calcium sulphoaluminate cement, calcium sulfate and added to the composition listed by other degree it is any other Reactive cement) and activator component B.Reactive powdery components A is comprising aluminosilicate mineral material (including the C through thermal activation Class flying dust), the blend of the material of calcium sulphoaluminate cement and calcium sulfate.Activator component B include alkali metal chemical activating agent or Its mixture, it can be powder or the aqueous solution.Reactive the powdery components A and activator component B combined forms this hair The reactive mixture of the geo-polymer cementitious composition of bright this preferred embodiment.

Table B represent the binding agent of incorporation Table A and the preferred embodiment of other compositions theoretical density (100 to 160 pounds/it is vertical Preferred density in the range of super superficial) formula.

Table B

Table C represents to mix the binding agent of Table A and the lightweight density of other compositions (preferably in 10 to 125 pounds/cubic feet of models Enclose interior density) optimization formula.

Table C

Table D represent the incorporation binding agent of Table A, coarse aggregate and other compositions lightweight density or theoretical density (preferably 40 to Density in the range of 160 pounds/cubic feet) some optimization formulas.

Table D

The long-term free shrink that the geo-polymer of some embodiments of the present invention is glued binder mixtures (shrinks measurement Start between after mixing forms aqueous mixture about 1 to about 4 hour) it is about 0.3% or less, preferably less than about 0.2%, more preferably less than about 0.1%, most preferably less than about 0.05%.As it was previously stated, according to some embodiments of the present invention, warp The aluminosilicate mineral material of thermal activation, calcium sulphoaluminate cement, calcium sulfate appropriate selection source and amount, and used with appropriate amount Appropriate selection alkali metal activator between cooperative interaction help to make Material shrinkage to reach minimum.

Known aluminosilicate mineral material (such as flying dust) polymerize with the geology of alkali metal activator (such as alkali-metal citrate) Thing reaction is related to reaction rate extremely fast, wherein due to the exothermic reaction being related to, discharges the heat of significant quantity.It is described quick Exothermic reaction speed results in alumino-silicate compound, and material is gelled and hardened as quick as thought (in big few minutes).Class As, it is also known that the interaction of calcium sulphoaluminate cement and calcium sulfate is related to reaction rate extremely fast, wherein because heat release is anti- Answer, discharge the heat of significant quantity.As the result of Fast exothermic reaction, the hydrated product of formation calcium sulphoaluminate compound, material Material is gelled and hardened (also in big few minutes) as quick as thought.Extremely short setting time be in some applications it is problematic, because Short working life (working life) is provided for it, the short working life (working life) causes quick in actual field is applied The processing of the material of solidification and the obvious difficulty of arrangement.Moreover, substantial amounts of heat can cause not as caused by reacting Fast exothermic Desired thermal expansion and the cracking of subsequent material and destruction.

Those skilled in the art will be expected, if due to by aluminosilicate mineral material, alkali metal activator, calcium sulphoaluminate water Mud and calcium sulfate mix, and exothermic reaction (the i.e. aluminosilicate mineral of such as flying dust for making both of the aforesaid quickly solidify The reaction of matter and alkali metal salt, and the reaction of calcium sulphoaluminate cement and calcium sulfate) occur simultaneously, then compared to wherein as above two Reaction independently occurs, and high heat produces and quick solidification would not want in undesirable horizontal situation, resulting materials Ground release even more heats, it is undesirable that ground is gelled and hardened more quickly.Using all four above-mentioned reactive group In the embodiments of the invention divided, it was unexpectedly found that really not so.When by aluminosilicate mineral material, alkali metal activator, When calcium sulphoaluminate cement and calcium sulfate mix, compared to two-part reaction system known to above-mentioned two, resulting materials Heat release is less, and with the gelling and firm time extended.This cooperative interaction seemingly occurred between these four raw materials Unpredictable consequence is provided in some embodiments of the invention.

Find in some embodiments of the invention another unexpected result is that, when aluminosilicate mineral material and alkali Metal activation agent Material shrinkage observed when being reacted with calcium sulphoaluminate cement and calcium sulfate one significantly reduces.Referring to example Following example such as the four reactive component systems of the present invention and the comparative example 1-4 only containing both or three in reactive component Non-invention system comparison.Even if when relatively small amounts of calcium sulphoaluminate cement and calcium sulfate are contained in aluminosilicate When in the reactive mixture of salt mineral matter and activator, what also generating material shrank significantly reduces.

Very it was unexpectedly found that, some embodiments of the present invention geo-polymer be glued adhesive composition The amount of middle calcium sulphoaluminate cement influences the Material shrinkage degree measured after material initial solidification.Also unexpectedly send out It is existing, in a given embodiment beyond some amount of calcium sulphoaluminate cement when, the Material shrinkage that occurs after material initial solidification Amount start to increase.

Table D1 show reflection control initial solidification after composition contraction ability some preferred embodiments into The amount divided.

Table D1

Also unexpectedly find, the ground of the amount of the calcium sulfate being present in mixture to some embodiments of the present invention The Material shrinkage degree of matter polymer cementitious composition, which has, to be significantly affected.

Table D2 shows that the amount of composition in some embodiments of the invention (can be used for the calcium sulfate of control Material shrinkage Amount/100 part calcium sulphoaluminate cement).

Table D2

For the alkali metal activator and other components of specified rate in the composition of some embodiments of the present invention, it has been found that The use of calcium sulfate dihydrate provides the maximally effective control for making Material shrinkage reach minimum.Dead plaster (anhydrous gypsum) Use with calcium sulfate hemihydrate also provides is glued binding agent group to the geo-polymer for reducing some embodiments of the present invention The excellent control of the Material shrinkage of compound.Calcium sulfate dihydrate and dead plaster (anhydrous gypsum) are calcium sulfate of the invention Preferred form.It is highly preferred that calcium sulfate is provided with fine granularity.

It has been unexpectedly found that the amount of alkali metal activator is glued the geo-polymer of some embodiments of the present invention The Material shrinkage degree of adhesive composition, which has, to be significantly affected.Table D3 show preferably to realize this benefit relative to glue Connect the alkali metal activator of the weight of material (aluminosilicate mineral material, calcium sulphoaluminate cement and calcium sulfate i.e. through thermal activation) % amounts composition amount.

Table D3

It was unexpectedly found that calcium silicates base hydraulicity cement (such as Portland cement) is mixed to some implementations of the present invention The dimensional stability of resulting materials is had adverse effect in the geopolymer formulation of example.Increase is added to this embodiment Geopolymer formulation in the amount of Portland cement can increase the contraction of resulting composition.Even if work as calcium sulphoaluminate water When mud, calcium sulfate and alkali metal chemical activating agent are present in this embodiment, also produced in the case where Portland cement be present The increase that green material is shunk.For instance, it has been found that incorporation is with solid adhesive material, (as used herein, " adhesive material " includes mixing The dried ingredients of thing, the mixture are included in the aluminosilicate through thermal activation in the reactive powder composition of some embodiments Salt mineral matter, all cement material and calcium sulfate) gross weight meter 15%, 33%, 52% and 74% Portland cement (base In dry weight) measured after material initial solidification 8 weeks material free shrinks are increased to about 0.15% respectively, 0.23%, 0.31% and 0.48%.

Therefore, in the embodiment that the contraction wherein as above measured is a problem, it is undesirable to be limited to theory, it is believed that addition ripple Special blue cement can negatively affect four fundamental reaction powder (aluminosilicate mineral material, calcium sulphoaluminate cement through thermal activation, Calcium sulfate and alkali metal chemical activating agent) between cooperative interaction.Therefore, wherein the contraction as above measured is the reality of a problem The geo-polymer cementitious composition for applying example does not preferably mix the Portland cement for being enough to produce this undesirable shrinkage degree.

In order to form adhesive composition, hybrid reaction powdery components A (aluminosilicate mineral material, sulphur through thermal activation Aluminous cement and calcium sulfate), activator component B (alkali metal chemical activating agent) and water, to be formed at about 0 DEG C to about 50 DEG C, Preferably from about 10 DEG C to about 35 DEG C of the initial temperature (temperature during first minute that composition is all present in mixture first Degree) under splicing slurry.As a result, geopolymeric reaction then occurs, so as to cause alumino-silicate geo-polymer to react The formation of species and the solidification of resulting materials and hardening.Meanwhile the hydration reaction of calcium sulphoaluminate phase and silicic acid calcium phase also occurs, from And cause the solidification and hardening of resulting materials.

The geopolymer formulation of the dimensionally stable of some currently preferred embodiments of the present invention has extremely low water demand, with Obtain brand-new state under can process mixture and produce hardening state under strong long life material.

In the case of in the absence of coarse aggregate, the geo-polymer of the dimensionally stable of some embodiments of the present invention, which is glued, to be glued Knot agent preferable water/total solid weight ratio be about 0.04 to about 0.25, preferably from about 0.04 to about 0.20, more preferably from about 0.05 to About 0.175, most preferably from about 0.05 to about 0.15.In the case where coarse aggregate be present, the size of some embodiments of the present invention is steady Preferable water/total solid ratio preferably less than about 0.125, more preferably less than about 0.10 of fixed geo-polymer binding agent, it is optimal Choosing is less than about 0.075.Total solid include based on anhydrous adhesive material, gather materials (such as sand or other gather materials), filler and other Solid additive.

Minimal amount of water is provided to realize chemical hydration and alumino-silicate geopolymeric reaction in such an embodiment.It is preferred that Ground, in the slurry, the weight ratio of water and powder adhesive material is about 0.17 to about 0.40, more preferably from about 0.2 to about 0.35, even More preferably from about 0.22 to 0.3.As used herein, " adhesive material " is defined as the aluminosilicate mineral material through thermal activation, sulphur aluminic acid Calcium cement and calcium sulfate, and may be added to that any other cement in reactive mixture.The amount of water depends on being present in glue Connect the needs of the single material in composition.

The solidification of the composition of this embodiment is characterised by initial and final setting time, such as uses ASTM C266 Measured by the Gilmore pins specified in test step.Final setting time is also corresponded to when concrete product (such as concrete surface Plate) time when being sufficiently hardened and can handle.

Generally, the geopolymeric reaction of the aluminosilicate mineral material (such as flying dust) through thermal activation is heat release.Anticipate again The other places discovery of material, in certain embodiments, flying dust, calcium sulphoaluminate cement, calcium sulfate and alkali metal chemical activating agent are as ground The part of matter polymerisation and cooperative interaction each other, so as to significantly decrease what is discharged by the material of generation exothermic reaction The speed and amount of heat.The type and its amount of appropriate selection calcium sulfate, the amount of calcium sulphoaluminate cement, appropriate selection alkali metal chemistry Activator and its measure speed and amount effective for reducing and minimizing the heat discharged due to consequential exothermic reaction.

Generally, the geopolymeric reaction of the aluminosilicate mineral material (such as flying dust) through thermal activation is also entered with quick speed OK, and fast gelation and the solidification of material are caused.Generally, when according to the single flying dust of prior art and alkali metal chemical activating agent During reaction, the gelling of material started in 2 to 3 minutes, and was less than after aqueous mixture is formed in 10 minutes and reaches final Solidification.

In a preferred embodiment of the invention, unexpectedly find, the alumino-silicate through thermal activation of such as flying dust Mineral matter, calcium sulphoaluminate cement, calcium sulfate and alkali metal chemical activating agent cooperate with phase each other as the part of geopolymeric reaction Interaction, so as to significantly increase the gelling time of resulting materials and final setting time.The type of appropriate selection calcium sulfate and The amount of its amount, calcium sulphoaluminate cement, and appropriate selection alkali metal chemical activating agent and its amount extend the gelling speed of resulting materials Rate and gelling time and final setting time.

For the alkali metal activator of specified rate in such an embodiment, it has been found that the amount for increasing calcium sulfate adds gained Geo-polymer is glued the gelling time of adhesive composition and final setting time.In addition, for giving in such an embodiment Quantitative alkali metal activator, it has been found that the granularity for increasing calcium sulfate adds gained geo-polymer splicing adhesive composition Gelling time and final setting time.In addition, in different types of calcium sulfate in the present compositions, it has been found that sulphur Sour calcium semihydrate provides the highest increase of the gelling time and final setting time of gained geo-polymer cementitious composition.It is right It is glued binding agent in the geo-polymer of some preferred embodiments, gelling time is about 20 to about 60 minutes, final setting time It is about 30 to about 120 minutes.Gelling time and final setting time are useful in actual field application, because they are provided The geo-polymer of this embodiment is glued longer opening and the process time of binding agent.

As used herein, the early strength of composition is characterised by, compressive strength is measured afterwards within 3 to 5 hours in solidification. In numerous applications, of a relatively high early stage compressive strength can be an advantage for adhesive material because its can bear it is higher Stress and without excessive deformation.High early strength is obtained to also increase and the processing that product is made and the related security of use Factor.Further, since obtaining high early strength, many materials and structure can carry in early stage, and allow support in early days it is non- Structure and structural loads.Generally, providing the increased chemical reaction of intensity in such a composition will be when having reached final solidification Between after period for persistently extending.

The geo-polymers of some embodiments of the present invention be glued binding agent can produce high early stage compressive strength and Final compressive strength.It can be produced for example, the geo-polymer of some this embodiments is glued binding agent after 1 to 4 hour About 500psi to about 4000psi compressive strength, about 1500 to about 5000psi compressive strength is produced at 24 hours later, About 3,500 to about 10000psi compressive strength is produced after 28 days.

In such an embodiment, when the amount of calcium sulfate is about the 10 to about 50 weight % of calcium sulphoaluminate cement, produce early Phase compressive strength dramatically increases.Also it has been unexpectedly found that the type of calcium sulfate is to the ground of some embodiments of the present invention The increase of the early stage compressive strength (≤24 hours) of matter polymer cementitious composition has significant impact.Have found, work as use During dead plaster (anhydrous gypsum), the highest increase of early stage compressive strength is produced.

In some embodiments it has been found that the smaller particle size of calcium sulfate produces the more rapid of early stage (≤24 hours) intensity Increase.When it is desirable that during intensity increase with the speed that is exceedingly fast, the preferred average particle size of calcium sulfate is about 1 to about 30 micron, more excellent About 1 to about 20 micron, most preferably from about 1 to about 10 micron of choosing.

Cementation reaction mixture

The cementation reaction mixture of some currently preferred embodiments of the present invention includes reactive powdery components A and activator group Divide B, its preferred scope is as shown in Table A.Reactive powdery components A includes the aluminosilicate mineral material through thermal activation, sulphur aluminic acid Calcium cement and calcium sulfate.Activator component B includes alkali metal chemical activating agent.

Preferably, cementation reaction mixture contains about 10 to about 40wt.% lime.However, the lime need not be The lime added respectively.On the contrary, chemical constituent of the lime sometimes as the aluminosilicate mineral material through thermal activation includes.

In addition to the aluminosilicate mineral material through thermal activation, calcium sulphoaluminate cement and calcium sulfate, cementation reaction powder It can include about 0 to about 5wt.% optional splicing additive (such as Portland cement).It is preferable, however, that Portland water is not present Mud, because incorporation Portland cement ash increase Material shrinkage, so that dimension stability is deteriorated.

C classes flying dust and other aluminosilicate mineral materials through thermal activation

In certain embodiments, the aluminosilicate mineral material through thermal activation is selected from flying dust, blast furnace slag, through thermal activation Clay, shale, metakaolin, zeolite, plaster, red mud, grinding rock and grinding clay brick.Preferably, they have greater than about 5 Weight % Al₂O₃Content.Clay or plaster are used generally after thermal activation, the thermal activation passes through at about 600 ° to about 850 It is heat-treated and carries out at a temperature of DEG C.The preferable aluminosilicate mineral material through thermal activation of this embodiment of the present invention has Preferably greater than about 10wt%, more preferably greater than about 15%, most preferably greater than about 20% high lime (CaO) in the composition contain Amount.Aluminosilicate mineral material most preferably through thermal activation is C class flying dusts, such as the flying dust obtained by burning coal power station.Flying dust With pozzolanic.

Pozzolanic material is defined as " siliceous or siliceous and aluminum material, itself having small by ASTM C618 (2008) Splicing value (cementitious value) or without splicing value, but under form in small, broken bits and in the case where moisture be present Chemically react and formed with the compound for being glued property with calcium hydroxide under ordinary temperature ".

In the cementation reaction powder blend of some embodiments of the present invention, flying dust is the preferably silicon through thermal activation Aluminium mineral material matter.As described below, flying dust (such as ASTM C618 (2008) marks of high oxidation calcium and aluminic acid calcium content are preferably comprised Accurate C classes flying dust).

Flying dust is the fine powder byproduct that is formed by burning of coal.The power plant power boiler of burning pulverized coal produces big portion Divide commercially available flying dust.These flying dusts are mainly by the residue of glass spherical particle and bloodstone and magnetic iron ore, charcoal, and cooled Some the crystallization phase compositions formed in journey.Structure, composition and the property of fly ash particle depend on coal texture and composition and shape Into the combustion process of flying dust.ASTM C618 (2008) standard points out the flying dust for two primary categories in concrete：C classes With F classes.This two classes flying dust is typically derived from different classes of coal, and the different classes of coal is the coal shape occurred in the geologic(al) period The result obtained by difference during.F classes flying dust is generally produced by burning anthracite or bituminous coal, and C classes flying dust generally by Lignite or ub-bituminous coal produce.

ASTM C618 (2008) standard mainly distinguishes F classes and C class flying dusts according to pozzolanic.Therefore, in ASTM In C618 (2008) standard, the main specifications difference between F classes flying dust and C class flying dusts is the SiO in composition₂+Al₂O₃+Fe₂O₃ Least limit.The SiO of F class flying dusts₂+Al₂O₃+Fe₂O₃Least limit be 70%, C class flying dusts SiO₂+Al₂O₃+Fe₂O₃'s Least limit is 50%.Therefore, F classes flying dust has more pozzolanic activity than C class flying dusts.Although do not marked in ASTM C618 (2008) Explicitly pointed out in standard, but C classes flying dust preferably has high oxidation calcium (lime) content.

In addition to pozzolanic, due to free lime (calcium oxide), C classes flying dust, which generally has, is glued property.When F classes When being mixed with single water, it is rarely what is be glued.The presence of high oxidation calcium content is supplied to C classes flying dust to be glued property, so as to Calcium silicates and calcium aluminate hydrate are resulted in when it is mixed with water.As can be seen that in following instance in the excellent of the present invention Select in embodiment, it has been found that C classes flying dust provides excellent result.

In such an embodiment, the aluminosilicate mineral material through thermal activation includes C class flying dusts, preferably comprises about 50 to about Aluminosilicate mineral material of the parts by weight through thermal activation of 100 parts of C classes flying dust/100, it is highly preferred that the sial through thermal activation Hydrochlorate mineral matter includes about 75 parts to about 100 parts of aluminosilicate mineral material of C classes flying dust/100 part through thermal activation.

In those or other preferred embodiments, it is possible to use other kinds of flying dust, such as F class flying dusts.Preferably, it is glued At least about 50wt.% of the aluminosilicate mineral material through thermal activation in reactive powder is C class flying dusts, and remainder is F Class flying dust or any other aluminosilicate mineral material through thermal activation.It is highly preferred that in cementation reaction powder through thermal activation Aluminosilicate mineral material about 55 to about 75wt.% be C class flying dusts, and remainder be F classes flying dust or any other through heat The aluminosilicate mineral material of activation.Preferably, the aluminosilicate mineral material through thermal activation is the C class flying dusts of about 90 to about 100%, Such as 100% C class flying dusts.

It is micro- that the particle mean size of the aluminosilicate mineral material through thermal activation of some embodiments of the present invention is preferably less than about 100 Rice, most preferably less than about more preferably less than about 50 microns, even more preferably less than about 25 microns, 15 microns.

Preferably, binder mixtures of the invention have the at most about 5 parts of sial of metakaolin/100 part through thermal activation Hydrochlorate mineral matter.It is highly preferred that the binding agent of the present invention does not include the metakaolin of significant quantity.Have found the presence of metakaolin The water demand of some mixtures is added, therefore the use of metakaolin polymerize in the geology of some currently preferred embodiments of the present invention It is undesirable in thing adhesive composition.

Generally existing mineral matter is quartz (SiO in flying dust₂), mullite (Al₂Si₂O₁₃), cacoclasite (Ca₂Al₂SiO₇), bloodstone (Fe₂O₃), magnetic iron ore (Fe₃O₄) etc..In addition, the alumina silicate polymorphic being typically found in rock (such as sillimanite, kyanite and andalusite, whole threes are by molecular formula Al for thing mineral matter₂SiO₅Represent) be also normally present in it is winged In ash.

Flying dust can also include another source of calcium sulfate or sulfate ion, and it is by the mixed of some embodiments of the present invention In polymer composition.

In some preferred embodiments, the fineness of flying dust, which is preferably such that, is retained in 325 mesh sieves (system of the U.S. less than about 34% Row) on, such as according to ASTM test steps C-311 (2011) (" Sampling and Testing Procedures for Fly Ash as Mineral Admixture for Portland Cement Concrete are " (" as portland cement concrete Mineral adulterating agent flying dust sampling and test step ")) it is measured.Available for the flat of the fly ash material in this embodiment Equal granularity is preferably less than about 50 microns, more preferably less than about 35 microns, even more preferably less than about 25 microns, most preferably less than about 15 microns.The flying dust is preferably dried recovery due to its self-solidifying property and used.

There is C classes flying dust the following representativeness listed by table E to form made from ub-bituminous coal.The flying dust is due to its self-solidifying Matter and be preferably dried recovery and use.

Table E

Preferable suitable F class flying dusts have the following composition listed by table F.

Table F

Hydraulic cement

Hydraulic cement for purposes of the present invention is following cement：It is solidifying that chemistry occurs when the cement contacts with water Gu reacting (hydration), and (solidification) not only is solidified in the presence of water, also form water resistance product.

Hydraulic cement includes but is not limited to alumina silicate cement (such as Portland cement), calcium sulphoaluminate cement, calcium aluminate-based Cement and calcium aluminum fluoride cement.

Calcium sulphoaluminate (CSA) cement

Calcium sulphoaluminate cement forms the composition of the geo-polymer adhesive composition of some embodiments of the present invention.Sulphur aluminium Sour calcium (CSA) cement is different classes of with aluminous cement (CAC) or calcium silicates base hydraulicity cement (such as Portland cement) Cement.CSA cement is that (it is Portland based on calcium sulphoaluminate rather than calcium aluminate (it is the basis of CAC cement) or calcium silicates The basis of cement) hydraulic cement.Calcium sulphoaluminate cement is made by clinker, and the clinker includes Ye ' elimite (Ca₄ (AlO₂)₆SO₄Or) it is used as main phase.

Be present in preferable calcium sulphoaluminate cement other mainly mutually may include it is following in one or more：Silicic acid two Calcium (C₂S), tetra calcium aluminoferrite (C₄) and calcium sulfate AFCompared to Portland cement, calcium sulphoaluminate cement it is relatively low Lime requirement reduce energy expenditure and greenhouse gases from cement prepare discharge.In fact, calcium sulphoaluminate cement can be than ripple Manufactured at a temperature of special blue cement is low about 200 DEG C, therefore reduce further energy and greenhouse gas emission.It is present in available Ye ' elimite phases (Ca in calcium sulphoaluminate cement in some embodiments of the present invention₄(AlO₂)₆SO₄Or) Measure and be preferably from about 20 to about 90wt%, even more preferably about 30 to about 75 wt%, most preferably from about 40 to about 60wt%.

The preferred composition of the present invention includes about 1 to about 200 parts by weight, more preferably from about 2.5 to about 100 parts by weight, even More preferably from about 2.5 to about 50 parts by weight, even more preferably from the calcium sulphoaluminate cement of about 5 to about 30 parts by weight (pbw), with every 100pbw The aluminosilicate mineral material meter through thermal activation.

Amount for the calcium sulphoaluminate cement in the composition of some embodiments of the present invention can be based on being present in CSA cement In active Ye ' elimite phases (Ca₄(AlO₂)₆SO₄Or) amount and adjust.

Portland cement

Include of the invention one of aluminosilicate mineral material, alkali metal chemical activating agent, calcium sulphoaluminate cement and calcium sulfate The geopolymer formulation of the dimensionally stable of a little embodiments shows extremely low Material shrinkage magnitude.So will rationally naturally It is expected that if another binder material with good dimensional stability is additionally incorporated in the mixture of the present invention, gained The overall material contraction of composition and dimensional stability will remain in that relatively low and acceptable.For example, pure Portland cement base The contraction of cementitious composition has been determined as gathering with the geology almost formed than the flying dust by activating using alkali-metal citrate Compound binding agent shrinks lower magnitude.However, very unexpectedly, it has been found that Portland cement is added to and includes silicon Aluminium mineral material matter, alkali metal chemical activating agent, calcium sulphoaluminate cement and calcium sulfate dimensionally stable of the invention composition The Shrinkage behavior of resulting composition is had adverse effect.Have found, Portland cement is polymerize added to the geology of the present invention Compositions add the contraction of resulting composition.It was observed that contraction size as Portland cement is in resulting composition Amount increase and increase.The result is very surprising and unexpected, and it, which is highlighted, works as other kinds of water The chemical phase occurred during the geo-polymer adhesive composition for the dimensionally stable that mud and/or chemical addition agent introduce the present invention The extremely complex property of interaction.Based on the understanding, Portland cement is not mixed in some currently preferred embodiments of the present invention. It is contemplated, however, that when being needed in the case of certain increase of acceptable Shrinkage behavior, can be in certain embodiments using a certain amount of Portland cement.The practical limit of the amount of Portland cement depends on the amount of the acceptable adverse effect to Shrinkage behavior, But in some currently preferred embodiments of the present invention, the parts by weight of the Portland cement comprising no more than 15 parts by weight/100 are through thermal activation Aluminosilicate mineral material.

The inexpensive and widely available property of limestone, shale and other natural materials causes Portland cement to turn into the whole world In one of material of last century widely used least cost.

As used herein, " Portland cement " is calcium silicates base hydraulicity cement.ASTM C150 define Portland cement For " prepared by by crushing the clinker being substantially made up of hydraulic calcium silicate, hydraulic cement was (not only by being reacted with water And harden, also form the cement of water resistance product), it usually contains the calcium sulfate of one or more forms as interground addition ". As used herein, " clinker " is the caused sintered material when the original stock of predetermined composition is heated into high temperature Ball (about 0.2 to about 1.0 inch of diameter [5-25mm]).

Aluminous cement

When the low water content slurry of the especially flying dust containing significant quantity need not be higher compressive strength when, calcium aluminate water Mud (CAC) is the another type of hydraulicity water of the component for the reactive powder blend that can form some embodiments of the present invention Mud.

Aluminous cement (CAC) is also commonly referred to as alumina cement or alumina cement.There is aluminous cement high-alumina to contain Amount, about 30-45wt% is preferable.The aluminous cement of higher purity is also commercially available, and wherein alumina content may be up to about 80wt%.The aluminous cement of these higher purity is often prohibitively expensive relative to other cement.By some implementations of the present invention The aluminous cement fine grinding used in the composition of example, enters aqueous phase, so as to which entringite and its occurs to be advantageous to aluminate The quick formation of his calcium aluminate hydrate.Surface area available for the aluminous cement in this embodiment will be greater than about 3, 000cm²/ gram, preferably from about 4,000 to about 6,000cm²/ gram, as surveyed by Blaine Surface Area Methodologies (ASTM C204) .

Has there are several manufacture methods to prepare aluminous cement in the whole world.Preferably, for manufacturing aluminous cement Primary raw material is alumina and limestone.A kind of manufacture method for preparing aluminous cement is described below.Crush and do first Dry bauxite mine, then grinds together with limestone.Then the dried powder comprising alumina and limestone is fed to rotary kiln.Make The fuel in kiln is used as by the use of powdery low ash coal.Reaction between alumina and limestone occurs in kiln, is collected in the lower end of kiln Fused product, and be poured into the groove for being arranged on bottom.Melting clinker is quenched to form the particle of clinker using water, then will The particle of clinker is sent to bedding plant.Then by the particulate abrasive into required fineness to prepare final cement.

Generally, several calcium aluminate compounds can be formed in the manufacturing process of aluminous cement.The main chemical combination formed Thing is usually monocalcium aluminate (CaOAl₂O₃, also referred to as CA).Other calcium aluminates and calcium silicate compound formed may include 12CaO·7Al₂O₃(also referred to as C₁₂A₇)、CaO·2Al₂O₃(also referred to as CA₂), dicalcium silicate (2CaOSiO₂, referred to as C₂S)、 Gehlenite (dicalcium alumina silicate) (2CaOAl₂O₃·SiO₂, referred to as C₂AS).Also it can be formed and contained There are other several compounds of relatively high proportion of iron oxide.These include calcium ferrite (such as CaOFe₂O₃Or CF and 2CaO Fe₂O₃Or C₂), and calcium aluminoferrite (such as tetra calcium aluminoferrite (4CaOAl F₂O₃·F_e2O₃Or C₄AF)、6CaO·Al₂O₃·2Fe₂O₃ Or C₆AF₂) and 6CaO2Al₂O₃·Fe₂O₃Or C₆A₂F).Other a small amount of components being typically found in aluminous cement include oxygen Change magnesium (MgO), titanium dioxide (TiO₂), sulfate and alkali.

Aluminous cement can have the one or more in foregoing phase.With monocalcium aluminate (CaOAl₂O₃Or CA) and/or C 12 A 7 (12CaO7Al₂O₃Or C₁₂A₇) as main phase aluminous cement in some embodiments of the invention To be particularly preferred.In addition, aluminic acid calcium phase can in crystalline form and/or amorphous form obtain.CIMENTFONDU (or HAC FONDU), SECAR51 and SECAR71 be with monocalcium aluminate (CA) as the commercially available aluminous cement of main cement phase some Example.TERNAL EV are with C 12 A 7 (12CaO7Al₂O₃Or C₁₂A₇) commercially available aluminic acid as main cement phase One example of calcium cement.

When calcium aluminate (CAC) cement is in the present invention in use, they can partly substitute aluminous cement.The present invention's The amount of the aluminous cement substituted in the composition of some embodiments can be total weight of calcium sulphoaluminate cement and aluminous cement The at most about 49wt% of amount.

Calcium aluminum fluoride

Calcium aluminum fluoride has chemical formula 3CaO3Al₂O₃·CaF₂.Calcium aluminum fluoride is generally made in the following way：With institute The mineral for obtaining product are changed into 3CaO3Al₂O₃·CaF₂Amount combined lime, alumina and fluorite, and in 00 DEG C of 1,200 °-Isosorbide-5-Nitrae At a temperature of burning gained mixture.Calcium aluminum fluoride cement can be optionally used in the present invention, but generally in many examples It is undesirable.

Calcium sulfate

Calcium sulfate forms the composition of the geo-polymer adhesive composition of certain embodiments of the present invention.Although calcium sulfate (such as calcium sulfate dihydrate) will be reacted with water, but it does not form water resistance product, and it is not qualified as the present invention's The hydraulic cement of purpose.The preferable sulfuric acid calcium type that can be used in the present invention includes calcium sulfate dihydrate, calcium sulfate half Hydrate and dead plaster (sometimes referred to as calcium sulfate anhydrite).These calcium sulfate may be from natural source or industry system .When using calcium sulfate as described herein, calcium sulfate can be with other bases of the cementitious composition of the preferred embodiments of the present invention This component cooperative interaction, thereby assisting in makes Material shrinkage reach minimum, and is given to final material simultaneously other are available Property.

The calcium sulfate of different shape form can be used in each embodiment of the present invention.Have found, this reality of the invention The property of the geo-polymer binding agent and composite of applying example significantly depend on based on chemical composition, granularity, crystal habit and The type of the calcium sulfate of chemical treatment and heat treatment.In other properties, the geo-polymer binding agent of this embodiment Solidification behavior, intensity advance the speed, final compressive strength, Shrinkage behavior and it is resistance to it is anti-thread breakage can by select be formulated in sulfuric acid The appropriate sources of calcium and adjust.Therefore, the selection of the type of calcium sulfate used in the composition of those embodiments is based on final Using sought balance of properties.

Although the calcium sulfate (predominantly semihydrate, dihydrate and anhydrous gypsum) of all three forms can be used for this hair In four reactive component mixtures of some bright embodiments, with provide compared to only containing in reactive component both or three The setting time longer following comparative example 1-4 of person and the benefit of Geng Gao compressive strength, it has been found that in each reality of the present invention Apply three kinds of different sulfuric acid calcium forms in example have relative to each other to setting time and compressive strength it is different and unexpected Effect.

It is well known that the most solvable chemical species of calcium sulfate is semihydrate, it is relatively low solubility form afterwards Dihydrate, it is the anhydrous gypsum of relatively insoluble form afterwards.All three forms are known per se under proper condition in water Property medium in the solidification matrix of dihydrate chemical species (formed), and the setting time of known solidification form and compressive strength are abided by Follow their solubility order.For example, be equal in every other situation, and in the case of being used alone as unique solidification material, Semihydrate generally has most short setting time, and anhydrous gypsum has most long setting time (during the solidification generally extremely grown Between).

Very unexpectedly, it has been found that primarily or entirely there is most long coagulate using the embodiment of calcium sulfate hemihydrate Though the time, primarily or entirely there is most short setting time using those embodiments of calcium sulfate anhydrite.Equally exceed Ground is expected, compared to the main embodiment for using dihydrate form, primarily or entirely using dead plaster (anhydrous gypsum) Each embodiment there is bigger early stage compressive strength.

In the geopolymer formulation of other embodiment, it is possible to use the calcium sulfate of two or more types is total to Mixed thing, with relative to the setting time of those embodiment regulation compositions of the calcium sulfate for primarily or entirely using single type and Early stage compressive strength property.When using this blend, the type of calcium sulfate used may depend on their chemical composition, Granularity, crystal shape and form and/or surface treatment and difference.

Have found, the granularity and form of calcium sulfate used significantly affect the geo-polymer of some embodiments of the present invention It is glued the early strength of adhesive composition and the increase of final strength.General, it has been discovered that the calcium sulfate of smaller particle size provides early The faster increase of phase intensity.When it is desirable that during intensity increase with the speed that is exceedingly fast, the preferred average particle size of calcium sulfate is about 1 To about 100 microns, more preferably from about 1 to about 50 micron, most preferably from about 1 to about 20 micron.In addition, it has also been found that there is more fine granularity Calcium sulfate reduce Material shrinkage.

Have further been discovered that, calcium sulphoaluminate cement and other existing raw material components for specified rate, the amount of calcium sulfate Increase (but not being excessively to increase) produce some embodiments of the present invention geo-polymer binding agent early stage compressive strength Increase.When the amount of calcium sulfate is about the 10 to about 50 weight % of calcium sulphoaluminate cement, the most aobvious of early stage compressive strength is produced The increase of work.

Unexpectedly find, the amount of existing calcium sulfate proportional to the calcium sulphoaluminate cement in mixture is to this hair The Material shrinkage degree of the geopolymer formulation of some bright embodiments, which has, to be significantly affected.Preferably, those embodiments Amount with the calcium sulfate of about 5 to about 200 parts by weight in terms of 100 parts by weight calcium sulphoaluminate cement.For most effectively controlling this The Material shrinkage of geopolymer formulation in kind embodiment, the amount of calcium sulfate are calculated as with 100 parts by weight calcium sulphoaluminate cement About 10 to about 100 parts by weight, be more preferably calculated as about 15 to about 75 parts by weight with 100 parts by weight calcium sulphoaluminate cement, most preferably with 100 parts by weight calcium sulphoaluminate cement are calculated as about 20 to about 50 parts by weight.

For specified rate in the composition of some embodiments of the present invention alkali metal activator and other raw material components, It was found that the use of calcium sulfate dihydrate provides the maximally effective control for making Material shrinkage reach minimum.Dead plaster is (anhydrous Gypsum) and the use of calcium sulfate hemihydrate also provide adhesive composition be glued to the geo-polymer for reducing this embodiment Material shrinkage excellent control.

Selection for one or more types of the calcium sulfate in the composition of this embodiment is based in final application The balance of speed, contraction control and other properties needed for sought early strength is increased.

The calcium sulfate of part amount or whole amount can be as the calcium sulphoaluminate cement in the composition of many this embodiments Additive component and add.When the case, the amount for the calcium sulfate being added separately in the composition, which has subtracted, is contained in sulphur Equivalent in aluminous cement.

Calcium sulfate also may be included in the flying dust in some embodiments of composition.When the case, in the composition The amount for the calcium sulfate being added separately can be reduced.

The availability for the sulfate ion that can be contributed based on the other compositions being present in mixture and adjust and separately add The amount of the calcium sulfate added in the composition of some embodiments of the present invention.

Volcanic ash

Substantially seldom it is glued property or other without the volcanic ash for being glued property as itself having in an aqueous medium Optional silicate and aluminosilicate mineral material can be contained in some embodiments of the present invention as optional mineral additive Composition in.Various natural and artificial materials have been referred to as the pozzolanic material with pozzolanic.Pozzolanic material Some examples include silicon ash, float stone, perlite, diatomite, finely ground clay, fine grinding shale, fine grinding slate, fine grinding glass, solidifying ash Rock, volcanic soil and rice bran.All these pozzolanic materials can be used as some embodiments of the present invention in the form of alone or in combination Cementation reaction powder part.

Filler-gather materials, inorganic mineral filler and light filler

Although disclosed cementation reaction powder blend defines the cementitious composition of many embodiments of the present invention Quick coagulating component, but it will be understood by a person skilled in the art that other materials may depend on composition desired use and application and It is contained in composition.

One or more fillers of such as sand, fine aggregate, coarse aggregate, inorganic mineral filler and light filler can be used as Component in the geo-polymer formula of some embodiments of the present invention.In such an embodiment, these fillers are not preferably fire Mountain ash or the aluminosilicate mineral material through thermal activation.

Preferable inorganic mineral filler is dolomite, limestone, calcium carbonate, grinding clay, page in such an embodiment Rock, slate, mica and talcum.Generally, in the composition of some embodiments of the present invention, this filler has fine granularity, its It is preferred that average grain diameter is less than about 100 microns, preferably less than about 50 microns, more preferably less than about 25 microns.When in order to the present invention's Purpose with significant quantity using smectite clay and palygorskite and their mixture when, it is suitable inorganic ore deposit to be not considered as them Material filler.

As used herein, fine aggregate or sand be defined as usual particle mean size less than about 4.75mm (0.195 inch) (although Depending on application can be used other sizes) inorganic rock material.Preferable sand has about 0.1mm to about in the present invention 2mm particle mean size.In some embodiments of the invention, particle mean size is about 1mm or smaller fine sand is preferable filler.

Maximum particle size is about 0.6mm, preferably up to about 0.425mm, and particle mean size is about 0.1 to about 0.5mm, preferably from about 0.1mm is used for the sand about in the range of 0.3mm in the other embodiment of the present invention.It is preferred that the example of fine sand includes having the U.S. QUIKRETE the FINE No.1961 and UNIMIN5030 of screen size #70-#30 (0.2-0.6mm) predominant size.

The amount of size distribution and sand in formula assists the rheological behavior of the embodiment of control incorporation sand.Fine sand can To be glued with about 0.05 to about 4 sand/adhesive material (reactive powder) than the geo-polymer added to some embodiments In composition.When it is desirable that obtaining self-leveling material rheology, best sand/adhesive material ratio in formula is about 0.50 To in the range of about 2, most preferably from about 0.75 to about 1.5.

It is at least about 4.75mm (0.195 inch) that coarse aggregate, which is defined as particle mean size, e.g., from about 1/4 ' inch to about 1-1/2 The inorganic rock material of inch (0.64 to 3.81cm) (other sizes can be used although dependent on concrete application).Size is more than Gathering materials for about 1-1/2 inches (3.81cm) can also be used in some applications, such as concrete road surface.The shape of particle of coarse aggregate and Structure can have a variety of constructions, such as angular, coarse-texture, elongated, circular or smooth, or these combination.

Preferable coarse aggregate is made by mineral matter, as granite, basalt, quartz, cordierite (riolite), andesite, Tufa stone, float stone, limestone, dolomite, sandstone, marble, flint, flint, hard sand, slate, and/or genesis rock (gnessis).Preferably meet ASTMC33 (2011) and AASHTO M6/ available for the coarse aggregate in some embodiments of the present invention Specification described in M80 (2008) standard.

When coarse aggregate is included in the geo-polymer cementitious composition of some embodiments of the present invention, they preferably with About 0.25 to about 5/adhesive material (reactive powder) ratio use of gathering materials.Some embodiments of the present invention are with about 0.25 to about 1 Coarse aggregate/adhesive material ratio contain coarse aggregate.Some other embodiments of the present invention are with about 1 to about 3 coarse aggregate/splicing material Material ratio contains coarse aggregate.

Light filler has less than about 1.5, preferably less than about 1, more preferably less than about 0.75, most preferably less than about 0.5 Proportion.In some other preferred embodiments of the present invention, the proportion of light filler is less than about 0.3, more preferably less than about 0.2, Most preferably less than about 0.1.On the contrary, inorganic mineral filler preferably has about more than 2.0 proportion.The example of available light filler Son is float stone, vermiculite, clay, the expanded form of shale, slate and perlite, scoria, sintered expanded slag, cinder, glass microsphere, Synthesize ceramic microsphere, ceramic microspheres, lightweight polyphenyl ethene pearl, plastic hollow micro-balloons, expansion plastic pearl etc..Work as expansion plastic When pearl and hollow plastics ball are used in the composition of some embodiments of the present invention, due to their relatively low proportions and specifically Using they are used with appropriate amount (by weight).

When light filler is used to reduce the weight of some embodiments of the present invention, they can be with e.g., from about 0.01 to about 2, preferably from about 0.01 to about 1 filler/adhesive material (reactive explosive) is than using.The light filler of two or more types Combination can also be used for the present invention this embodiment in.

Although some embodiments of the present invention only contain sand as addition filler, other embodiment contain sand and Inorganic mineral filler and/or light filler.Inorganic mineral filler and light filler can be used as addition in other embodiment Filler.Moreover, other embodiment incorporation sand, the filler of inorganic mineral filler and light filler as addition.The present invention Other embodiment only contain inorganic mineral filler or light filler, and be free of sand, fine aggregate or coarse aggregate.In addition, contain The embodiments of the invention for having coarse aggregate can be wrapped with or without the one or more in following filler：Sand, light filler and nothing Machine mineral filler.Filler of the other embodiment substantially free of any addition

Alkali metal chemical activating agent

Alkali metal salt and alkali can be used as chemical activating agent, (like flying comprising the aluminosilicate mineral material through thermal activation with activation Ash), the reactive powdery components A of calcium sulphoaluminate cement and calcium sulfate.Lived for the alkali metal in some embodiments of the present invention Agent can be added in the form of liquid or solid.The preferable alkali metal chemical activating agent of this embodiment of the present invention is organic The metal salt of acid.Preferred alkali metal chemical activating agent is the alkali metal salt of carboxylic acid.Alkali metal hydroxide and alkali metal silicon Hydrochlorate is some other examples of the alkali metal chemical activating agent available for some embodiments of the present invention.Or alkali metal hydrogen Oxide and alkali silicate can be also applied in combination with carboxylic acid (such as citric acid), and the alumino-silicate through thermal activation is included to provide The chemical activation of the reactive powder blend of mineral matter, calcium sulphoaluminate cement and calcium sulfate.

In some embodiments of the invention, using with including the aluminosilicate mineral material through thermal activation, calcium sulphoaluminate water The alkali metal salt (such as sodium citrate or potassium citrate) of the citric acid of the reactive powder blend of mud and calcium sulfate combination provides Blend composition, the blend composition have relatively good mobility, and under environment temperature (about 20-25 DEG C) Or only rapid hardening after mixed material about under environment temperature.

The amount of the alkali metal salt (such as potassium citrate or sodium citrate) of citric acid is about 0.5 to about 10wt.%, preferably from about 1 to about 6wt.%, preferably from about 1.25 to about 4wt.%, more preferably from about 1.5 to about 2.5wt.%, most preferably from about 2wt.%, with 100 Cementation reaction component (the i.e. reactive powdery components A) meter of part some embodiments of the present invention.Thus, for example, for 100 pounds Cementation reaction powder, the potassium citrate and/or sodium citrate of about 1.25 to about 4 total poundage may be present.Preferable alkali gold It is potassium citrate and sodium citrate, particularly citric acid tri potassium monohydrate and anhydrous sodium citrate, lemon to belong to citrate Sour three sodium-hydrates, DisodiumHydrogen Citrate, citrate trisodium dihydrate, disodium citrate and sodium dihydrogen citrate.

Preferably, solidification activator is free of alkanolamine.And preferably, activator not phosphate-containing.

Solidify retarding agent

Such as organic compound of hydroxy carboxylic acid, carbohydrate, carbohydrate and starch is implemented for some of the present invention The preferred retarding agent of example.Organic acid (such as citric acid, tartaric acid, malic acid, gluconic acid, butanedioic acid, glycolic, malonic acid, fourth Acid, malic acid, fumaric acid, formic acid, glutamic acid, valeric acid, glutaric acid, gluconic acid, hydroxymalonic acid, glactaric acid, trihydroxybenzoic acid etc.) It can be used as the solidification retarding agent in the geo-polymer splicing adhesive composition of the dimensionally stable of some preferred embodiments.

Gluconic acid sodium salt also is used as organic solidification retarding agent in some embodiments of the present invention.Cellulose base organic polymer Thing (hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), ethyl cellulose (EC), Methylethylcellulose (MEC), carboxymethyl cellulose (CMC), carboxymethylethylcellulose (CMEC), carboxy methyl hydroxyethyl fiber Plain (CMHEC)) for the present invention composition some in other available retarding agent.

When in the composition that these cellulose base retarding agents are added to some embodiments of the present invention, except producing retardance Outside, it dramatically increases the viscosity of mixture.Preferably, inorganic acidic group retarding agent (such as borate or boric acid) is not existed with significant quantity Used in some currently preferred embodiments of the present invention, because they hinder mixing rheological, cause excessive weathering, and reduction pair The material adhesion strength of other base materials.

Other optional solidification controlling agents

Other optional solidifications control chemical addition agents include sodium carbonate, potassium carbonate, calcium nitrate, calcium nitrite, calcium formate, Calcium acetate, calcium chloride, lithium carbonate, lithium nitrate, lithium nitrite, aluminum sulfate, sodium aluminate, alkanolamine, polyphosphate etc..When these add Add agent as formula a part include when, except influence some embodiments of the present invention geo-polymer adhesive composition Solidification behavior outside, they also influence the rheology of the geopolymer formulation.

Optional material, fiber and scrim

Other optional materials and additive may be included in the geo-polymer binding agent group of some embodiments of the present invention In compound.These are included selected from following at least one member：Film forming redispersible polymer powder, film forming polymer latex point Granular media, defoamer and antifoaming agent, water-loss reducer, solidification controlling agent, contraction reduce adulterating agent, foaming agent and air entraining agent, organic and nothing Machine rheology control agent, viscosity modifier (thickener), weathering control (suppression) agent, corrosion control agent, wetting agent, colouring agent and/ Or the continuous fiber and reinforcement of pigment, discrete fibre, length, Fabric reinforcements, vinal and/or, glass fibre and/ Or other discrete reinforcing fibers.

Different types of discrete reinforcing fiber can mix is glued plate combination according to made from certain embodiments of the present invention In thing.By the material and such as polymeric material of polypropylene, polyethylene and nylon of the glass fibre of such as cement-based powder material coating Obtained scrim is to depend on the function and application of cement base products and can be used for the example of enhancing cement base products.

Preferably, the geo-polymer binding agent of many preferred embodiments of the invention is free of the cement kiln powder of significant quantity Dirt.Cement kiln dust (CKD) can produce in clinker preparation process in kiln.Dust is rich in alkali metal sulfates, halogen The granulate mixture through partial calcination and unreacted raw material, clinker dust and ash content of compound and other volatile matters.These Particle is captured by waste gas, and is collected in particulate matter control device (such as cyclone separator, bag house and electrostatic precipitator).

CKD is mainly formed by calcium carbonate and silica and (is similarly to cement kiln raw material), but alkali, chloride and sulfate Amount it is considerably higher generally in dust.From three kinds of different types of operations (by long wet, long dry and that there is precalciner alkali Leak informaton on road) CKD there are various chemically and physically characteristics.From CKD caused by the wet and long dry kiln of length by rich in alkali metal sulfates With the charging fines composition of the kiln through partial calcination of chloride.The dust collected from the alkali bypass of pre-calcined firing is often more Slightly, more through calcining, and also concentration has alkaline volatile matter.However, alkali bypass method contains the oxygen of maximum amount (by weight) Change calcium and minimum loss on ignition (LOI).Carry out the 2008IEEE/ of the Miami, FL of comfortable 19-22 days in May, 2008 In PCA50th Cement Industry Technical Conf. (the 50th technology in cement industry meeting of 2008IEEE/PCA) The Adaska of proposition et al. Beneficial Uses of Cement Kiln Dust's (advantageous use of cement kiln dust) The composition that table provides three kinds of different types of operations decomposes, and including the preferred chemical composition for I class Portland cements For comparing.

Superplasticizer and air entraining agent

Water reducer (superplasticizer) is preferred in the composition of some embodiments of the present invention.They can be to dry shape Formula is added in the form of a solution.Superplasticizer can assist to reduce the water demand of mixture.The example of superplasticizer includes poly- naphthalene sulphur Acid esters, polyacrylate, polycarboxylate, polyether-type polycarboxylate, lignosulphonates, melamine sulphonic acid ester, casein etc..Take Certainly in the type of superplasticizer used, superplasticizer (in terms of dried powder) and the weight ratio of reactive powder blend are about 5wt% or smaller, preferably from about 2wt% or smaller, preferably from about 0.1 to about 1wt%.

Superplasticizer based on polycarboxylic acids ester type polyethers chemistry is the most preferred diminishing of some embodiments of the present invention Learn adulterating agent.Most preferably polycarboxylic acids ester type polyethers superplasticizer, because they are advantageously implemented the of the invention each of the foregoing description Individual purpose.

Air entraining agent is added in the splicing slurry of some embodiments of the present invention, to be formed in situ bubble (foam).Draw Gas agent is preferably the surfactant for being used to deliberately trap microscopic bubble in concrete.Or air entraining agent is used for outside produce Foam, the foam are introduced into during married operation in the mixture of the composition of some embodiments, to reduce product Density.Preferably, in order to which outside produces foam, mixing air entraining agent (also referred to as liquid blowing agent), air and water, with suitable Foam is formed in foam-generating device.Can be steady by the foam of such as polyvinyl alcohol before foam is added in splicing slurry Determine agent and be added to foam.

The example of air entraining agent/foaming agent includes alkyl sulfonate esters, alkyl benzo sulphonic acid ester (alkylbenzolfulfonate) With alkyl ether sulfate ester oligomer etc..The details of the formula of these foaming agents is found in the Sucech being herein incorporated by reference United States Patent (USP) 5,643,510 in.

Air entraining agent (foaming agent) can be used, such as meet ASTM C260 " Standard Specification for Air- Entraining Admixtures for Concrete (standard specification of the bleed adulterating agent of concrete) " (August 1 in 2006 Day) described in standard air entraining agent.This air entraining agent is that well known to a person skilled in the art and be described in Kosmatka et al. " Design and Control of Concrete Mixtures (design and control of concrete mix) ", the 14th edition, Portland Cement Association, specific 8th chapter entitled " Air Entrained Concrete (air-entraining concrete) " is (in United States Patent (USP) Shen It please announce in No.2007/0079733A1 and quote).

Commercially available airentrapment material includes vinsol wood resin, sulfonation hydro carbons, aliphatic acid and resin acid, the virtue of aliphatic series substitution Base sulphonic acid ester (such as lignosulfonate salt and be usually taken anion or nonionic surfactant form many other interfaces Active material), sodium abietate, saturation or unrighted acid and its salt, surfactant (tenside), alkyl-aryl-group-sulphur Acid esters, phenol elhoxylate, lignosulphonates, resin soap, hydroxyl sodium stearate, lauryl sulfate ester, ABS (benzene sulfonamides Acid esters), LAS (linear alkyl benzene sulfonic acid ester), alkane sulfonic acid ester, polyxyethylated (phenyl) ether, polyxyethylated (benzene Base) ether sulfuric ester or its salt, polyxyethylated (phenyl) ether phosphate or its salt, protein material, alkenyl sulfosuccinic acid Ester, α-olefin sulfonate, the sodium salt of α-olefin sulfonate, or NaLS or dodecyl sodium sulfate and their mixing Thing.

Preferably, bleed (foaming) agent is about the 0.01 to about 1wt.% of the weight of overall cementitious composition.

Biopolymer or organic rheology control agent

Succinoglycan, enlightening spy glue (diutan gum), guar gum, polyvinyl glue, xanthans and cellulose ether are organic Compound is to serve as the biopolymer of hydrocolloid and rheology control agent in some embodiments of the invention.Synthesize organic poly- Compound (such as polyacrylamide, alkali swellable acrylic polymer, association acrylic polymer, acrylic acid/acrylamide Copolymer, hydrophobically modified alkali swellable polymer, height water-swellable organic polymer) it can be used as this embodiment Geo-polymer adhesive composition in rheology control agent and thickener.

Association type and non-association type rheology control agent and thickener can be used for the geo-polymer binding agent of this embodiment In composition.Cellulose base available for the rheology control in the geopolymer formulation of those embodiments of the present invention has The example of machine polymer include hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), Ethyl cellulose (EC), methylethylcellulose (MEC), carboxymethyl cellulose (CMC), carboxymethylethylcellulose (CMEC), Carboxymethyl hydroxyethyl cellulose (CMHEC).Above-mentioned organic rheology control agent and thickener are dissolved in cold water and hot water.Except control Outside prepared material rheology, these additives also function as water-loss reducer, material separation and infiltration (bleeding) is reached most It is small.

Inorganic rheology control agent

The geo-polymer cementitious composition of some embodiments of the present invention can also include the nothing for belonging to phyllosilicate race Machine rheology control agent.The example for the inorganic rheology control agent being particularly useful in those embodiments may include palygorskite, sepiolite, Smectite, kaolinite and illite.The example of especially available smectite clay is hectorite, saponite and montmorillonite.It is not of the same race The natural or chemically treated POLARGEL NF of class can also be used for controlling the rheology of the composition of those embodiments.It is this Additive also functions as water-loss reducer, and material separation and infiltration is reached minimum.Inorganic rheology control agent can in the absence of Addition is combined in the case of organic rheology control agent or with organic rheology control agent.

Film forming polymer additive

In some embodiments of the invention, preferable film forming redispersible polymer powder is latex powder.These are poly- Compound powder is that water is redispersible, and is made by being spray-dried aqueous polymer dispersions (latex).

Latex is emulsion polymer.Latex is the aqueous-based polymers dispersion being widely used in commercial Application.Latex is poly- The stabilising dispersions (colloid emulsion) of compound particulate in an aqueous medium.Therefore, it is rubber or plastic polymer particulate in water In suspension/dispersion.Latex can be natural or synthesis.

Latex is preferably by pure acrylic acid class, styrene rubber, styrene butadiene ribber, styrene-acrylonitrile copolymer acids, ethene The ethylene vinyl acetate of base acrylic compounds or acroleic acid esterification is made, and more preferably pure acrylic acid class.It is preferred that Ground, latex polymer are derived from selected from following at least one acrylic monomer：Acrylic acid, acrylate, methacrylic acid And methacrylate.For example, it is preferable to include following monomer for the monomer in emulsion polymerization：Methyl acrylate, acrylic acid second Ester, methyl methacrylate, butyl acrylate, 2-EHA, other acrylate, methacrylate and they Blend, acrylic acid, methacrylic acid, styrene, vinyltoluene, vinyl-acetic ester, the carboxylic acid than acetic acid higher level Vinyl esters (such as vinyl versatate base ester), acrylonitrile, acrylamide, butadiene, ethene, vinyl chloride etc., and they Mixture.

For example, latex polymer can be butyl acrylate/methylmethacrylate copolymer or 2-EHA/ Methylmethacrylate copolymer.Preferably, latex polymer is also derived from selected from following one or more monomers：Benzene second It is alkene, α-methylstyrene, vinyl chloride, acrylonitrile, methacrylonitrile, methacrylic acid urea groups ester, vinyl-acetic ester, branched Vinyl esters, itaconic acid, crotonic acid, maleic acid, fumaric acid, ethene and the C4-C8 conjugated dienes of tertiary monocarboxylic acid.

Weathering inhibitor

Waterproofing agent (such as silane, organosilicon, siloxanes, stearate) can be added to the glue of some embodiments of the present invention Composition is connect, to reduce the weathering possibility of material.The selected example of available weathering inhibitor includes octyl group triethoxy Silane, potassium methyl silicate, calcium stearate, butyl stearate, polymer stearate.These weathering controlling agents reduce water and passed through Transmission in the material of hardening, thereby making it possible to causing the salt of weathering and the migration of other soluble chemical product to reach minimum. Excessive weathering can cause the aesthetic feeling of difference, material damage and damage caused by the expansion reaction that salt accumulation and salt hydration occur It is bad, and the reduction with other base materials and the adhesion strength of face coat.

Defoamer

Defoamer can be added to the geo-polymer cementitious composition of some embodiments of the present invention, to reduce gassiness Amount, the increase strength of materials, increase are to the material adhesion strengths of other base materials, and surface aesthetic feeling is the application of major criterion wherein It is middle to produce flawless surface.Available for the suitable defoamer in the geopolymer formulation of some embodiments of the present invention Example include PEO, polyetheramine, polyethylene glycol, polypropylene glycol, alcoxylates, poly-alkoxyl compound, fatty alcohol Alcoxylates, hydrophobicity ester, tributyl phosphate, alkyl polyacrylates, silane, organosilicon, polysiloxanes, polyethers silica Alkane, acetylenic glycols, tetramethyl decynediol, secondary alcohol ethoxyl compound, silicone oil, hydrophobic silica, oil (mineral oil, vegetable oil, White oil), wax (paraffin, ester type waxes, fatty alcohol wax), acid amides, aliphatic acid, the polyether derivative etc. of aliphatic acid.

Initial slurry temperature

In some embodiments of the invention, the business that slurry provides adhesive composition is preferably formed under the following conditions The more controlled working time that industry uses, the condition provide the initial adhesion agent composition slurry temperature reduced and bonded to final The rise less than about 50 °F (28 DEG C) of agent composition slurry temperature, the rise of more preferably less than about 40 °F (22 DEG C), most preferably It is about 10 to about 240 minutes, more excellent to obtain improved temperature stability and more importantly less than about the rise of 30 °F (17 DEG C) Choosing about 60 to about 120 minutes, the gelling slowed down of most preferably from about 30 to about 60 minutes and final setting time.Initial slurry temperature Preferably from about room temperature.

The initial temperature of increase slurry adds the temperature rise rate carried out with reaction, and reduces setting time.Therefore, by It is designed as reducing temperature increase behavior of the mixture from initial slurry temperature, preferably some realities in the present invention in composite formula Apply and avoided in example preparing conventional flying dust base geological polymer adhesive composition to obtain institute in fast gelation and setting time The initial slurry temperature of 95 °F (35 DEG C) to 105 °F (41.1 DEG C).If initial slurry temperature is of a relatively high, make With this hair for increasing incipient gelation and final setting time (it transfers the business machinability for providing increased composition) The benefit for the heat endurance that bright many embodiments are obtained may be reduced slightly.

" initial temperature " is defined as after cementation reaction powder, activator and water are present in mixture first The temperature of master mix during first minute.Certainly, the temperature of master mix may be in first minute process Middle change, but in order to obtain preferable heat endurance, it is preferably maintained in the range of from about in 0 to about 50 DEG C of start temperature ranges, more excellent Choosing is maintained in about 10 to about 35 DEG C of start temperature ranges, is even more preferably maintained at about 15 to about 25 DEG C of initial temperature model In enclosing, environment temperature is preferably kept.

Material exothermic and temperature rise behavior

The composition of some embodiments of the present invention is advantageously obtained in material during cure stage and gently put Hot and low temperature rise.In this composition of some embodiments of the present invention, the maximum temperature rise occurred in material is preferably smaller than About 50 °F (28 DEG C), more preferably less than about 40 °F (22 DEG C), most preferably less than about 30 °F (17 DEG C).This prevent excessive thermal expansion With subsequent material cracking and destruction.The material for being related to big thickness in material is applied with wherein actual field is poured into a mould The mode of (material pour) is in use, the aspect becomes even more favourable.The geo-polymer cementitious composition of the present invention Thing is favourable in the particular aspects, because they show lower thermal expansion in actual field application and improved to heat The resistance of cracking.

Example

In this paper example, as described above, unless otherwise expressly stated, otherwise composition or the percentage of product formula It is weight percentage.Unless explicitly stated otherwise, the measurement otherwise reported also is amount about, for example, percentage about, weight, Temperature, distance or other properties.Moreover, unless otherwise noted, otherwise using being available from CTS cement companies (CTS Cement Company component of the FASTROCK500 board calcium sulphoaluminate cement as cementation reaction powder).FASTROCK500 has about 5 microns of particle mean size, and 95% in particle is thinner than about 25 microns.The FASTROCK500 Blaine fineness that measures is about 6780cm²/g.FASTROCK500 oxide composition is analyzed, and is shown in Table A A：

Table A A

The main phase being present in FASTROCK500 calcium sulphoaluminate cement used in example includesC₂S、C₄AF With

In all examples, unless otherwise noted, otherwise flying dust is the Campbell power plant from the western olive in the state of Michigan The C class flying dusts of (Campbell Power Plant, West Olive, MI).The flying dust has about 4 microns of particle mean size.Fly The Blaine fineness that measures of ash is about 4300cm²/g.Oxide for the C class flying dusts in these examples is formed such as Table A A institutes Show.

It is included in the calcium sulfate dihydrate in multiple examples to be available from U.S. Gypsum (United States Gypsum Company) particulate calcium sulfate dihydrate, be referred to herein as land plaster or particulate land plaster.Particulate land plaster has There is about 15 microns of particle mean size.

The dead plaster (anhydrous gypsum) being contained in some in example is to be available from U.S. Gypsum (United States Gypsum Company) SNOW WHITE board fillers.USG SNOW WHITE fillers are (usual by calcium sulfate For gypsum) high-temperature heat treatment prepared by insoluble form anhydrous gypsum.It has the chemical bond moisture of extremely low level, Preferably from about 0.35%.The particle mean size of USG SNOW WHITE fillers is about 7 microns.

It is included in the calcium sulfate hemihydrate in multiple examples to be available from U.S. Gypsum (United States Gypsum Company) USG HYDROCAL C-Base board calcium sulfate hemihydrates.HYDROCAL C-Base are with block The calcium sulfate hemihydrate of the α morphology forms of shape (blocky) crystal microstructure and low water demand.USG HYDROCAL C- Base has about 17 microns of particle mean size.

Coarse grain calcium sulfate dihydrate used (is being further referred to as thick land plaster or coarse grain gypsum herein in multiple examples Powder) with trade name USG BEN FRANKLIN AG board rubble cream by U.S. Gypsum (United States Gypsum Company) it is made.USG BEN FRANKLIN AG board gypsum is the coarse grain calcium sulfate that particle mean size is about 75 to about 80 microns Dihydrate.

It is from U.S. Gypsum (United States to be included in the particulate calcium sulfate dihydrate in multiple examples Gypsum Company) USG TERRA ALBA F＆P boards.USG TERRA ALBAF＆P fillers are that particle mean size is about 13 micro- The high-purity sulfuric acid calcium dihydrate of rice.

It is included in the QUIKRETE particulate No.1961 fine sands in some examples with the granularity as shown in table BB：

It is included in the UNIMIN5030 sand in some examples with the granularity as shown in table BB.

Potassium citrate or sodium citrate are added to one in the example of the cementitious composition of some embodiments of the present invention Alkali-metal citrate in a little, and serve as chemical activating agent, rheology modifier and solidification controlling agent.

The initial solidification time reported herein and final setting time use ASTM C266 using Gilmore pins (2008) standard measures.

The slump of the splicing geopolymer formulation of some embodiments of the present invention and flow behavior are tested by collapsing Characterize.The test used herein that collapses is about 10.16cm. (4 inches) using a diameter of about 5.08cm. (2 inches) and length Hollow circular cylinder, the hollow circular cylinder are kept vertically, and one open end is located on smooth plastic surface.Use splicing Mixture fills the cylinder until top, scrapes flat top surface to remove excessive slurry mix afterwards.Then it is soft perpendicular The cylinder is directly lifted, so that slurry comes out from bottom, and is sprawled on frosting and forms circular cake.Then cake is measured Diameter, and be recorded as the slump of material.As used herein, the composition with good flow behavior produces bigger slump Value.By with 1 to 10 evaluation of scale slurry fluidity, so as to characterize the flowing of slurry, wherein 1 value represents the flowing of extreme difference Behavior, 10 value represent excellent flow behavior.

By measuring the length change of prism-shaped sample according to ASTM C928 (2009) testing standard, so as to characterize such as this Material shrinkage (herein also referred to as " shrinking ") used in text.4 is small after single raw material components (including water) are brought together Constantly, initial length measurement is carried out.When 8 weeks after component (including water) is brought together, finally measured.Initial measurement Difference divided by initial length between final measurement are multiplied by 100%, obtain the contraction as percentage.According to ASTM C157 (2008) standard, 1 inch of x1 inches (cross section) length is made and changes prism-shaped sample (in herein also referred to as rod).

Reach destruction by testing 2 inches of x2 inch x2 inch cubes under compression, surveyed according to ASTM C109 (2008) Method for testing measures the compressive strength of material as used herein.After hardening and solidify in sealed plastic bag until when testing, Cube is stripped from brass die.Test cube when about 4 hours after casting, about 24 hours, about 7 days and about 28 days Body.In some instances, after the solidifications in 28 days in polybag are completed, cube was subjected to saturation up to 7 days.By these cubes Body takes out from water and after dry tack free, just tests these cubes under compression under saturation conditions.

By the way that slurry is placed in insulating vessel, and thermocouple recording materials temperature is used, so as under half adiabatic condition Measure slurry temperature rise behavior used herein.

Many in example, which is shown, includes aluminosilicate mineral material (flying dust), calcium sulphoaluminate cement, sulphur through thermal activation The physics of the geo-polymer cementitious composition of the exploitation of some embodiments of the present invention of sour calcium and alkali metal chemical activating agent Property.This illustrates incorporation calcium sulphoaluminate cement and calcium sulfate and alkali metal chemical activating agent to some embodiments of the present invention Exploitation geo-polymer cementitious composition Material shrinkage behavior, early stage compressive strength, final compressive strength, heat release behavior With the influence of coagulating property.

The composition of some embodiments of the present invention is advantageously obtained in material during cure stage and gently put Hot and low temperature rise.In such a composition, the maximum temperature rise occurred in material is preferably less than about 50 °F (28 DEG C), more preferably small In about 40 °F (22 DEG C), still more preferably less than about 30 °F (17 DEG C).This prevent excessive thermal expansion and subsequent material cracking and Destroy.When material in a manner of being related to the material cast (material pour) of big thickness in the application of wherein actual field to use When, the aspect becomes even more favourable.The geo-polymer cementitious composition of the invention studied as described below is in the spy Fixed aspect is favourable, because they show lower thermal expansion and the resistance to thermal cracking improved in actual field application.

The composition of the invention of some embodiments of the present invention also obtain long setting time, with provide it is good can Processability.Application for some embodiments of the present invention, extremely short setting time is problematic, because short material work Life-span (working life) causes the obvious difficulty for the material that the equipment being related in being applied using actual field and tool processes are quickly solidified.

The comparative example of geo-polymer cementitious composition known to example 1-

Following example shows the physical property of the contrast cementitious composition comprising C classes flying dust and alkali-metal citrate. Test result shows Shrinkage behavior, early stage and final compressive strength and the solidification behavior of the cementitious composition shown in table 1.Institute There are three kinds of mixtures to be activated using potassium citrate, and contain different amounts of sand.All three mixtures have about 100 weight The C classes flying dust of part and total adhesive material of about 100 parts by weight.In other words, all adhesive materials are C class flying dusts.

Figure 1A shows the Shrinkage behavior for the cementitious composition studied in comparative example 1.

Measurement is started to shrink at when 4 hours from raw material is mixed and cast.It can be observed, by alkali metal lemon The flying dust composition of acid salt activating shows high amount of contraction.It was found that after solidifying 8 weeks under about 75 °F/50%RH, measure Maximum collapse is up to about 0.75%.The increase of sand content reduces shrinkage degree, but overall shrinkage still remain in it is high It is horizontal.This high-caliber Material shrinkage make it that material is completely unsatisfactory for most of construction applications.It should be noted that For most of Application in Building, the contraction more than about 0.10% is considered as high and undesirable.

Initial flow behavior, slump and the early stage cracking behavior of material

Table 2 shows the initial flow behavior and slump for the cementitious composition studied in comparative example 1.

The flying dust composition activated using alkali-metal citrate has good stream in about 0.75 sand/cement than lower Dynamic behavior.When sand/cement ratio increases to about 1.5, slurry loses its mobility to small degree.In about 2.5 sand/water Under mud ratio, mixture becomes extremely hard, and does not have flow behavior.

Figure 1B shows the photo of the mixture #1 studied in comparative example 1 slump cake.When drying, slump cake produces bright Aobvious cracking.The beginning of crackle occurs after the test that collapses in less than about 30 minutes in cake.In the drying of subsequent material and hardening When, the quantity and flaw size of crackle increase.

Setting time

Table 3 shows the solidification behavior for the cementitious composition studied in comparative example 1.

Cementitious composition in the example has solidification behavior extremely fast.Formed water-based raw material is blended together It is less than about in 5 minutes after slurry, all mixtures are extremely fast gelled and lose flow behavior.

Compressive strength

Table 4 shows the compressive strength behavior for the cementitious composition studied in comparative example 1.All flying dust compositions are about About 7000psi compressive strength increase is showed more than at 28 days.

Example 2- comparative examples

The early stage dimensional stability of contrast cementitious composition of the case study comprising flying dust and alkali-metal citrate With crack-resistant property.Table 5 shows the raw material composition of studied blend composition.Mixture is activated using sodium citrate, and Contain different amounts of sand.Mixture has the C classes flying dust of about 100 parts by weight and total adhesive material of about 100 parts by weight.Change speech It, all adhesive materials are C class flying dusts.

The early stage cracking behavior of material

Fig. 2A shows the photo of the slump cake for the mixture studied in comparative example 2.When drying, slump cake produces obvious Cracking.The beginning of crackle occurs after the test that collapses in less than about 30 minutes in cake.In the drying of subsequent material and hardening, The quantity and flaw size of crackle rise appreciably.

The compressive strength behavior of the composition of comparative example 2

Table 5A shows the compressive strength behavior of the mixture in comparative example 2.The early stage compressive strength of composition is relatively It is low, 500psi was less than about at 4 hours, 2000psi was less than about at 24 hours.As shown afterwards in instances, use is equal Water/cement than embodiments of the invention geopolymer formulation produce in these identical early stages it is considerably higher Compressive strength., can be by adjusting the combination for embodiments of the invention as shown in the example of the specific embodiment of the present invention Type and amount, the amount of calcium sulphoaluminate cement of calcium sulfate in thing, and the type of alkali metal activator easily adjust with measuring Early stage compressive strength.

Example 3：Comparative example

The early stage dimensional stability of contrast cementitious composition of the case study comprising flying dust and alkali-metal citrate With crack-resistant property.Table 5 shows the raw material composition of studied blend composition.

The early stage cracking behavior of material

Fig. 3 A show the photo of the slump cake for the mixture studied in comparative example 3.When drying, slump cake produces obvious Cracking.The beginning of crackle occurs after the test that collapses in less than about 30 minutes in cake.

The compressive strength behavior of the composition of comparative example 3

Table 5B shows the compressive strength behavior of the mixture in comparative example 3.The early stage compressive strength of composition is relatively It is low, 500psi was less than about at 4 hours, and be less than about 1500psi.As shown in the example after embodiments of the invention, Can be by adjusting type and amount, the amount of calcium sulphoaluminate cement for the calcium sulfate in composition of the invention, and alkali metal work The type of agent adjusts early stage compressive strength with measuring.

Shrinkage behavior

Fig. 3 B show the Shrinkage behavior of the pole early stage of the cementitious composition in comparative example 3.

Since raw material is mixed and cast when 1 hour the measurement of pole early-age shrinkage.Use alkali metal lemon The flying dust composition of acid salt activating shows high amount of contraction.It was found that after solidifying 8 weeks under about 75 °F/50%RH, measure Maximum collapse is more than about 1%.This high-caliber Material shrinkage make it that material is unsatisfactory for most of construction applications 's.In most of Application in Building, the contraction more than about 0.10% is considered as undesirable height.

Example 4：Calcium sulphoaluminate cement is added to flying dust-comparative example

This example shows the physical of the cementitious composition comprising flying dust, calcium sulphoaluminate cement and alkali-metal citrate Matter.This have studied the incorporation of calcium sulphoaluminate cement to the contraction comprising flying dust and the cementitious composition of alkali-metal citrate and resists Cracking influence.

Table 6 and 7 shows each splicing mixture 1-4 studied in this example raw material composition.In each mixture The amount of calcium sulphoaluminate cement used is the about 20wt% to about 80wt% of flying dust weight in composition.

Initial flow behavior, slump and the early stage cracking behavior of material

Table 8 show the binary blend of the flying dust studied in example 4 and calcium sulphoaluminate cement initial flow behavior and Collapse.All mixtures studied have good flow behavior and big cake diameter, as collapsed what is observed in test.

Fig. 4 A show the photo of the slump cake for the mixture 1 and 2 studied in example 4.Fig. 4 B and 4C respectively illustrate reality The photo of the slump cake for the mixture 3 and 4 studied in example 4.When drying, all slump cakes produce obvious cracking.By original Material mixes about 10 minutes afterwards, and the cracking in cake starts to begin to occur.In the drying of subsequent material and hardening, crackle Quantity and flaw size rise appreciably.The mixture 1 of calcium sulphoaluminate cement with minimum amount produces minimal amount of split Change.Calcium sulphoaluminate cement is added to the flying dust composition activated with alkali-metal citrate and produces the unstable material of size, The material tends to overcracking in drying and hardening.

Shrinkage behavior

Casting rectangular prism configuration sample, to characterize the Shrinkage behavior of studied mixture.Fig. 4 D are shown in mixture 1st, mixture 2 (sample 2-1 and 2-2), mixture 3 (sample 3-1 and 3-2) and mixture 4 (sample 4-1 and 4-2) (by it is left extremely It is right) in a mold after casting the sample of about 4 hours mixtures obtained photo.Fig. 4 D show all casting prism-shapeds Sample cracking in a mold.Extremely significantly received (before the demoulding) in a few hours after all rods are cast in mold body Contract cracking.Crack width is measured, in the sample aging of about 24 hours, the contraction total amount of these mixtures was determined over about 1.0%.

Example 5

The purpose of the research is mixed in geo-polymer adhesive composition of the research in some embodiments of the present invention Enter the influence of different amounts of calcium sulfate dihydrate (particulate land plaster).

Table 9 and 10 shows that the geo-polymer studied in this example is glued the raw material composition of mixture.The example The amount of calcium sulphoaluminate cement used is equal to the about 40wt% of flying dust weight in blend composition.Calcium sulfate dihydrate is (thin Grain land plaster) horizontal (the about 25wt% of the weight of calcium sulphoaluminate cement, about 50wt%, about 75wt% peace treaties in different amounts 100wt%) make an addition in studied blend composition.It is held constant at for the water in the example/adhesive material ratio 0.25。

Initial flow behavior, slump and the early stage cracking behavior of material

Table 11 shows that is studied in example 5 includes flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate gypsum Powder) and alkali-metal citrate some embodiments of the present invention geo-polymer cementitious composition initial flow behavior and Slump characteristic.Can clear view arrive, all blend compositions studied are respectively provided with good Self-leveling and flow behavior, such as Collapse shown in cake diameter big in testing.It is especially noted that under as little as about 0.25 water/adhesive material ratio, Also this big slump value and Self-leveling behavior can be obtained.

Fig. 5 A show the slump of the geo-polymer cementitious composition for some embodiments of the present invention studied in example 5 The photo of cake.The slump cake of the example does not produce any cracking when drying, unlike without calcium sulfate dihydrate (land plaster) Comparative example 4 splicing mixture occur as.Therefore, by calcium sulfate dihydrate (particulate land plaster) incorporation comprising winged The mixture that is glued of ash, calcium sulphoaluminate cement and alkali-metal citrate provides the dimensionally stable with excellent crack-resistant property Geo-polymer cementitious composition.

Shrinkage behavior

Fig. 5 B show the contraction of the geo-polymer cementitious composition for some embodiments of the present invention studied in example 5 The figure of behavior.The main purpose of the research is to study incorporation calcium sulphoaluminate cement and particulate calcium sulfate dihydrate form Influence of the calcium sulfate to the Shrinkage behavior of the geo-polymer cementitious composition of some embodiments of the present invention.

From raw material is mixed to start to shrink at measurement when about 4 hours forming water paste.About 75 °F/ Under 50%RH while curing materials, measurement Material shrinkage was of about the total duration of 8 weeks.

It can be drawn the following conclusions by the research and Fig. 5 B：

Incorporation calcium sulfate dihydrate (particulate land plaster) also includes flying dust, calcium sulphoaluminate cement and alkali metal lemon to improvement The crack-resistant property and dimensional stability of the geo-polymer cementitious composition of some embodiments of the present invention of lemon hydrochlorate have aobvious Writing influences.With even before the demoulding comparative example 4 (not having calcium sulfate dihydrate) of cracking contraction rod on the contrary, including sulphur The contraction rod of the example 5 of sour calcium dihydrate (particulate land plaster) is stable, and does not show before or after the demoulding in rod Unacceptable dimensional stability or undesirable contraction cracking sign.

Include the sheet of flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate land plaster) and alkali-metal citrate The geo-polymer cementitious composition of some embodiments of invention measures maximum collapse significantly lower than only containing flying dust and alkali gold Belong to the contrast cementitious composition (example 1) of citrate measures maximum collapse.For example, compared to only containing flying dust and alkali metal About 0.75% maximum collapse of the control mixture (example 1) of citrate, includes flying dust, calcium sulphoaluminate cement, calcium sulfate The geo-polymer cementitious composition of some embodiments of the present invention of dihydrate (particulate land plaster) and alkali-metal citrate There is thing the maximum between about 0.07% to about 0.13% to measure contraction.Thus, it can be concluded that the sulphur by particulate land plaster form Sour calcium dihydrate helps extremely to show added to the cementitious composition comprising flying dust, calcium sulphoaluminate cement and alkali-metal citrate Writing ground reduces Material shrinkage.

Under about 25wt% low calcium sulfate dihydrate (particulate land plaster) amount, solidify 8 weeks under 75 °F/50%RH Afterwards, it is about 0.13% to measure maximum collapse.Calcium sulfate (particulate gypsum in the cementitious composition of some embodiments of the present invention Powder) amount further increase pole significantly reduce Material shrinkage.Under about 50wt% calcium sulfate (particulate land plaster) amount, measure Maximum Material shrinkage is reduced to about 0.08%.Similarly, measured in about 75wt% to about 100wt% calcium sulfate (particulate land plaster) Under, measure maximum Material shrinkage or even be further reduced to about 0.07%.

Heat release and slurry temperature rise behavior

Fig. 5 C are heat release and the slurry of the geo-polymer cementitious composition for some embodiments of the present invention studied in example 5 Material temperature rises the figure of behavior.Include flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate land plaster) and alkali metal citric acid The cementitious composition of the example 5 of salt shows extremely gentle temperature rise behavior.Gentle heat release in cure stage process in which materials With low-temperature-rise for prevent material excessive thermal expansion and subsequent cracking and destruction be effective.When material is with wherein actual existing It is related to the mode of material cast of big thickness in the application of field in use, the aspect becomes even more favourable.Studied in the example Some embodiments of the present invention geo-polymer cementitious composition be disclosed as be in the particular aspects it is highly advantageous, because The resistance to thermal cracking that will be produced lower thermal expansion in actual field application for them and improve.

Setting time

Table 11 shows the solidification of the geo-polymer cementitious composition for some embodiments of the present invention studied in example 5 The bar chart of time.

All cementitious compositions studied in example 5 have quick solidification behavior, and final setting time is about 20 to about 40 Minute.Include the present invention of flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate land plaster) and alkali-metal citrate Some embodiments exploitation cementitious composition have it is more visible only comprising flying dust and alkali-metal citrate than in example 1 Contrast the relatively longer setting time of cementitious composition.For the contrast glue comprising flying dust and alkali-metal citrate of example 1 Composition is connect, final setting time is about 15 minutes.Extremely short setting time applies some implementations in the present invention for some It is problematic in example, because it provides short working life (working life), the short working life (working life) causes The processing of material quickly solidified in actual field application and the obvious difficulty of arrangement.

In embodiments of the invention shown in this example, unexpectedly find, when by aluminosilicate mineral material, alkali When metal activation agent, calcium sulphoaluminate cement and calcium sulfate mix, gained reaction is less than the exothermic heat of reaction of two difference, And gelling time and firm time are obviously prolonged.

It has also been found that when aluminosilicate mineral material and alkali metal activator together with calcium sulphoaluminate cement and calcium sulfate it is anti- At once, significantly reducing with Material shrinkage, such as described above in paragraphs.

Compressive strength

Table 12 shows that is studied in example 5 includes flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate gypsum Powder) and alkali-metal citrate some embodiments of the present invention exploitation geo-polymer cementitious composition compressive strength Behavior.

Case study incorporation calcium sulphoaluminate cement and the calcium sulfate of particulate land plaster form to the present invention some The early stage of the geo-polymer cementitious composition of the exploitation of embodiment and the influence of final compressive strength behavior.As shown by data is such as Under：

The compressive strength of the geo-polymer cementitious composition of some embodiments of the present invention continues to increase with the time.

Early stage (about 4 hours and about 24 hours) intensity of mixture is with the amount of calcium sulfate (land plaster) in cementitious composition Increase and increase.

It polymerize using the calcium sulfate dihydrate of particulate land plaster form as the geology of some embodiments of the present invention In the case of the component of thing cementitious composition, 4 hours early stages compressive strength of material is more than about 1500psi.In addition, containing higher Amount particulate land plaster form the mixture 3 of calcium sulfate dihydrate and 4 hours compressive strengths of mixture 4 be about More than 3000psi.

In the geo-polymer that the calcium sulfate using particulate land plaster form is studied as some embodiments of the present invention In the case of the component of cementitious composition, early stage (i.e. 24 hours) compressive strength of material is more than about 3500psi.In addition, contain The mixture 3 of calcium sulfate (particulate land plaster) and 24 hours compressive strengths of mixture 4 of higher amount be about 4500psi with On.

28 days compressive strengths of all geo-polymer cementitious compositions of some embodiments of the present invention are high, and exceed 5000psi.28 days compressive strengths of mixture 1 to 3 are about 6000psi or bigger.

Example 6

The purpose of the research is mixed in geo-polymer adhesive composition of the research in some embodiments of the present invention Enter the influence of different amounts of calcium sulfate dihydrate (particulate land plaster).

Table 14 shows that the geo-polymer studied in the example is glued the raw material composition of mixture.The mixture of the example The amount of calcium sulphoaluminate cement used is equal to the 40wt% of flying dust weight in composition.In each blend composition studied In, it is horizontal in different amounts (125wt%, 150wt%, 175wt% and 200wt% of the weight of calcium sulphoaluminate cement and to fly 50,60,70 and 80wt% of ash) addition calcium sulfate dihydrate (particulate land plaster).For water/adhesive material in the example Than being held constant at 0.25.Also the super plasticising of QUIKRETE commerical grade fine sand No.1961 and BASF CASTAMENT FS20 is added Agent.

Initial flow behavior, slump and the early stage cracking behavior of material

Table 15 shows that is studied in example 6 includes flying dust, calcium sulphoaluminate cement, calcium sulfate (particulate land plaster) and alkali gold Belong to initial flow behavior and the slump characteristic of the geo-polymer cementitious composition of some embodiments of the present invention of citrate.

All blend compositions studied are respectively provided with good Self-leveling, flow behavior and big cake diameter, such as collapse What is observed in test.Even under as little as about 0.25 water/adhesive material ratio, big collapse and Self-leveling behavior can be also obtained.

Compared to the splicing mixture of the comparative example 4 without calcium sulfate dihydrate (land plaster), the slump cake of the example Any cracking is not produced when drying.Thus, it can be concluded that by calcium sulfate dihydrate (particulate land plaster) incorporation comprising winged The geo-polymer cementitious composition for being glued mixture and dimensionally stable being provided of ash, calcium sulphoaluminate cement and alkali-metal citrate Thing, the geo-polymer cementitious composition have the crack-resistant property excellent when drying.

Shrinkage behavior

Fig. 6 A show the contraction of the geo-polymer cementitious composition for some embodiments of the present invention studied in example 6 Behavior.Result from the example shows incorporation calcium sulphoaluminate cement and particulate calcium sulfate dihydrate and alkali metal lemon The collaboration of the Shrinkage behavior of the geo-polymer cementitious composition of exploitation of the hydrochlorate on some embodiments of the present invention influences.

From raw material is mixed to start to shrink at measurement when about 4 hours forming water paste.About 75 °F/ Under 50%RH while curing materials, measurement Material shrinkage was of about the total duration of 8 weeks.

Following important conclusion can be drawn by the research and Fig. 6 A：

The calcium sulfate dihydrate for mixing particulate land plaster form includes flying dust, calcium sulphoaluminate cement and alkali metal to improvement The crack-resistant property and dimensional stability of the geo-polymer cementitious composition of some embodiments of the present invention of citrate have Significantly affect.With even before the demoulding comparative example 4 (not having calcium sulfate) of cracking contraction rod on the contrary, including calcium sulfate two The contraction rod complete stability of the example 6 of hydrate (particulate land plaster), and do not produce any crackle before or after the demoulding.

Include the sheet of flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate land plaster) and alkali-metal citrate The geo-polymer cementitious composition of some embodiments of invention measures maximum collapse significantly lower than only containing flying dust and alkali gold Belong to the cementitious composition (example 1) of citrate measures maximum collapse.For example, compared to only including flying dust and alkali metal lemon About 0.75% maximum collapse of the mixture (example 1) of hydrochlorate, includes flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate The geo-polymer cementitious composition of some embodiments of the present invention of (particulate land plaster) and alkali-metal citrate has about The maximum collapse of 0.09% to about 0.12%.Therefore, calcium sulfate dihydrate (particulate land plaster) is added to and includes flying dust, sulphur The cementitious composition of aluminous cement and alkali-metal citrate helps to significantly reduce Material shrinkage.

Increase being slightly increased for the maximum collapse of gypsum powder quantity generation material under level used in this example.Observable Arrive, under about 125wt% gypsum powder quantity, Material shrinkage is about 0.09%.Gypsum powder quantity, which increases to about 200wt%, causes material Contraction increases to about 0.12%.

Heat release and slurry temperature rise behavior

Fig. 6 B show the heat release of the geo-polymer cementitious composition for some embodiments of the present invention studied in example 6 With slurry temperature rise behavior.It is observed that comprising flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate land plaster) and The cementitious composition of the example 6 of alkali-metal citrate only shows extremely gentle temperature rise behavior.

Gentle heat release and low-temperature-rise in cure stage process in which materials for prevent material excessive thermal expansion and with Cracking and destruction afterwards is effective.When material in a manner of being related to the material cast of big thickness in the application of wherein actual field to make Used time, the aspect become even more favourable.The geo-polymer for some embodiments of the present invention studied in the example is glued It is highly advantageous that composition, which is disclosed as in the particular aspects, because they will produce lower heat in actual field application Expansion and the resistance to thermal cracking improved.

Setting time

Table 16 is shown comprising flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate land plaster) and alkali metal lemon The setting time of the geo-polymer cementitious composition of some embodiments of the present invention studied in example 6 of lemon hydrochlorate.

All cementitious compositions studied in this example show the final setting time of about 35 to about 45 minutes.Compared to it Under, the contrast cementitious composition comprising flying dust and alkali-metal citrate of example 1 was with extremely fast final of about 15 minutes Setting time.

Compressive strength

What table 17 showed example 6 includes flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate land plaster) and alkali The early stage of the geo-polymer cementitious composition of the exploitation of some embodiments of the present invention of metal citrate and final compression Intensity behavior.

By the research, following observation can be drawn：

The compressive strength of the geo-polymer cementitious composition for some embodiments of the present invention studied in the example is at any time Between and continue to increase.

In the geo-polymer that the calcium sulfate using particulate land plaster form is studied as some embodiments of the present invention In the case of the component of cementitious composition, early stage (i.e. 4 hours) compressive strength of material is more than about 2500psi.In addition, mixture 1 to 34 hours compressive strengths are about more than 3000psi.

In the geo-polymer that the calcium sulfate using particulate land plaster form is studied as some embodiments of the present invention In the case of the component of cementitious composition, early stage (i.e. 24 hours) compressive strength of material is more than 4000psi.

28 days compressive strengths of the geo-polymer cementitious composition for some embodiments of the present invention studied in the example It is high, and more than 5000psi.28 days compressive strengths of the mixture 1 to 3 of the calcium sulfate containing particulate land plaster form are More than 6000psi.

Example 7

The purpose of the research is mixed in geo-polymer adhesive composition of the research in some embodiments of the present invention Enter the influence of different amounts of calcium sulfate dihydrate (particulate land plaster).

The example compares control mixture 1 without calcium sulfate dihydrate and comprising calcium sulphoaluminate cement and particulate The mixture 2,3 and 4 of calcium sulfate dihydrate.

The example compares control mixture 1 without calcium sulfate dihydrate and comprising calcium sulphoaluminate cement and particulate The mixture 2,3 and 4 of calcium sulfate dihydrate.

Table 18 shows that the geo-polymer studied in the example is glued the raw material composition of mixture.The mixture of the example The amount of calcium sulphoaluminate cement used is equal to the 80wt% of flying dust weight in composition.In the blend composition studied, Horizontal addition calcium sulfate dihydrate (particulate land plaster) is measured with following：0wt%, 10wt% of the weight of calcium sulphoaluminate cement, 20wt% and 30wt% (it is 0,8,16 and 24wt% of flying dust).For water/adhesive material in the example than keeping constant For 0.30.Also QUIKRETE commerical grade fine sand No.1961 and BASF CASTAMENT FS20 superplasticizers are added.

Initial flow behavior, slump and the early stage cracking behavior of material

Table 19 shows that is studied in example 7 includes flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate gypsum Powder) and alkali-metal citrate some embodiments of the present invention geo-polymer cementitious composition initial flow behavior and Slump characteristic.

All blend compositions studied have good flow behavior and big cake diameter, such as institute in the test that collapses It was observed that.Even under as little as about 0.3 water/adhesive material ratio, big collapse and Self-leveling behavior can be also obtained.

Fig. 7 A show, the slump of the control mixture 1 of the example 7 without any calcium sulfate dihydrate (particulate land plaster) Cake produces obvious cracking when drying.Fig. 7 B show, the geo-polymer cementitious composition of some embodiments of the present invention of example 7 The slump cake of the mixture 2,3 and 4 of thing does not produce any cracking under excellent condition.

Shrinkage behavior

Fig. 7 C show the receipts of the geo-polymer cementitious composition for some embodiments of the present invention studied in the example The data that indention is.

From raw material is mixed to start to shrink at measurement when about 4 hours forming water paste.About 75 °F/ Under 50%RH while curing materials, measurement Material shrinkage was of about the total duration of 8 weeks.

The research shows as follows：

Contraction rod with the comparative example 4 (not having calcium sulfate) of cracking even before the demoulding is on the contrary, (thin comprising calcium sulfate Grain land plaster) example 7 contraction rod complete stability, and do not produce any crackle before or after the demoulding.

Compared to about 0.75% of control mixture composition (example 1) only containing flying dust and alkali-metal citrate Maximum collapse, include the sheet of flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate land plaster) and alkali-metal citrate The geo-polymer cementitious composition of some embodiments of invention has the maximum collapse less than about 0.07%.

Compared to the Comparative composition (mixture 1) for only including flying dust, calcium sulphoaluminate cement and alkali-metal citrate About 0.19% measures maximum collapse, includes flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate land plaster) and alkali gold Belong to the geo-polymer cementitious composition (mixture 2,3 and 4) of some embodiments of the present invention of citrate measures maximum Shrink with the maximum collapse less than about 0.07%.

Heat release and slurry temperature rise behavior

Fig. 7 D show the heat release of the geo-polymer cementitious composition for some embodiments of the present invention studied in example 7 With slurry temperature rise behavior.Include flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate land plaster) and alkali metal citric acid The cementitious composition of the example of salt shows gentle temperature rise behavior.Gentle heat release in cure stage process in which materials and Low-temperature-rise for prevent material excessive thermal expansion and subsequent cracking and destruction be effective.When material is with wherein actual field It is related to the mode of material cast of big thickness in use, the aspect becomes even more favourable.Studied in the example It is highly advantageous that the geo-polymer cementitious composition of some embodiments of the present invention, which is disclosed as in the particular aspects, because The resistance to thermal cracking that they will produce lower thermal expansion and improve in actual field application.

Setting time

Table 20 shows the control mixture 1 of the geo-polymer cementitious composition of example 7 and the mixture 2,3 of the present invention With 4 setting time.

All cementitious compositions show solidification behavior extremely fast.However, include flying dust, calcium sulphoaluminate cement, sulfuric acid The mixture 2,3 and 4 of the invention of calcium dihydrate (particulate land plaster) and alkali-metal citrate has than only including flying dust The relatively longer setting time with the contrast cementitious composition (example 1) of alkali-metal citrate.Compared to only contain flying dust and The final setting time extremely fast of about 15 minutes of the control mixture composition (example 1) of sodium citrate, includes flying dust, sulphur The geo-polymer cementitious composition mixture 2 of some embodiments of the present invention of aluminous cement, land plaster and sodium citrate, 3 and 4 final setting time is about 60 to about 90 minutes.

Compressive strength

Table 21 shows that is studied in example 7 includes flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate gypsum Powder) and alkali-metal citrate some embodiments of the present invention exploitation geo-polymer cementitious composition compressive strength Behavior.

Following observation can be drawn：

The compressive strength of the geo-polymer cementitious composition for some embodiments of the present invention studied in the example is at any time Between and continue to increase.

Compared to the early stage compressive strength of the cementitious composition of some embodiments of the present invention comprising land plaster and final Compressive strength (mixture 2 to 4), the early stage compressive strength of the control mixture composition (mixture 1) without calcium sulfate and most Whole compressive strength is lower.

Early stage (4 hours and 24 hours) compressive strength of the geo-polymer cementitious composition of some embodiments of the present invention Increase with the increase of the amount of calcium sulfate dihydrate (particulate land plaster) in material.

Using geo-polymer glue of the calcium sulfate dihydrate (particulate land plaster) as some embodiments of the present invention In the case of the component for connecing composition, 24 hours early stages compressive strength of material is more than about 1500psi.The 24 of mixture 3 and 4 are small When compressive strength be more than about 2500psi.

All geology polymerization of some embodiments of the present invention comprising flying dust, calcium sulphoaluminate, land plaster and sodium citrate 28 days compressive strengths of thing cementitious composition are high, and are more than about 5000psi.Comprising (weight of calcium sulphoaluminate cement) about 28 days compressive strengths of the mixture 4 of the land plaster of 30wt% amount are more than about 6000psi.

Example 8

The purpose of the research is mixed in geo-polymer adhesive composition of the research in some embodiments of the present invention Enter the influence of different amounts of calcium sulfate dihydrate (particulate land plaster).

This example shows include flying dust, calcium sulphoaluminate cement, particulate calcium sulfate dihydrate (i.e. gypsum or land plaster) With the physical property of the geo-polymer cementitious composition of the exploitation of some embodiments of the present invention of alkali-metal citrate.Table 22 show that the geo-polymer studied in the example is glued the raw material composition of mixture.Institute in the blend composition of the example The amount of calcium sulphoaluminate cement is equal to the about 80wt% of flying dust weight.In the blend composition studied, to measure as follows Add land plaster：The weight of calcium sulphoaluminate cement 40wt%, 50wt%, 60wt% and 80wt% (its for flying dust 32,40, 48 and 64wt%).0.30 is held constant at for the water in the example/adhesive material ratio.Add QUIKRETE commerical grade fine sands No.1961 and BASF CASTAMENT FS20 superplasticizers.

Initial flow behavior, slump and the early stage cracking behavior of material

Table 23 shows that is studied in example 8 includes flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate gypsum Powder) and alkali-metal citrate some embodiments of the present invention geo-polymer cementitious composition initial flow behavior and Slump characteristic.

All blend compositions studied are respectively provided with good Self-leveling, flow behavior and big cake diameter, such as collapse Fall what is observed in test.It is especially noted that under as little as about 0.3 water/adhesive material ratio, can also obtain This big slump and Self-leveling behavior.

The slump cake of all four mixtures comprising calcium sulfate dihydrate (particulate land plaster) under excellent condition, and Do not produce cracking.

Shrinkage behavior

Fig. 8 A show the contraction of the geo-polymer cementitious composition for some embodiments of the present invention studied in example 8 Behavior.From raw material is mixed to start to shrink at measurement when about 4 hours forming water paste.About 75 °F/50% Under relative humidity (RH) while curing materials, measurement Material shrinkage was of about the total duration of 8 weeks.

Following important conclusion can be drawn by the research and Fig. 8 A：

With even before the demoulding comparative example 4 (not having calcium sulfate) of cracking contraction rod on the contrary, including calcium sulfate two The contraction rod complete stability of the example 8 of hydrate (particulate land plaster), and do not produce any crackle before or after the demoulding.

Compared to about 0.75% of control mixture composition (example 1) only containing flying dust and alkali-metal citrate Maximum collapse, include the sheet of flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate land plaster) and alkali-metal citrate The geo-polymer cementitious composition of some embodiments of invention has the maximum collapse of about 0.07% to about 0.18%.

Calcium sulfate dihydrate (particulate land plaster) amount is increased above into certain level has the function that to increase Material shrinkage. For example, under about 40wt% gypsum powder quantity (mixture 1), about 0.07% is always punctured into, under about 60wt% gypsum powder quantity (mixture 3), total contraction increase to about 0.13% value, under about 80wt% gypsum powder quantity (mixture 4), are always collapsible into one Step increases to about 0.18% value.

Compare the contraction test result from example 7 and example 8, the preferable calcium sulfate that minimum Material shrinkage is provided be present Dihydrate (particulate land plaster) measures scope.The amount scope of calcium sulfate dihydrate (particulate land plaster) seems to be these realities About the 10 to about 50wt.% of the calcium sulphoaluminate cement weight for the cementitious composition studied in example.

Heat release and slurry temperature rise behavior

Fig. 8 B show the heat release of the geo-polymer cementitious composition for some embodiments of the present invention studied in example 8 With slurry temperature rise behavior.Include flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate land plaster) and alkali metal citric acid The cementitious composition of the example of salt only shows extremely gentle temperature rise behavior.This prevent excessive thermal expansion and subsequent material Cracking and destruction.When material by wherein actual field application in be related to big thickness material cast in a manner of in use, the side Face becomes even more favourable.The geo-polymer cementitious composition for some embodiments of the present invention studied in the example is disclosed as It is highly advantageous in the particular aspects, because they will produce lower thermal expansion and raising in actual field application To the resistance of thermal cracking.

Setting time

Table 24 shows the solidification of the geo-polymer cementitious composition for some embodiments of the present invention studied in example 8 Time.

All cementitious compositions studied in the example show solidification behavior extremely fast.Compared to only containing flying dust With the final setting time extremely fast of about 15 minutes of the control mixture composition (example 1) of sodium citrate, comprising flying dust, The ground of some embodiments of the present invention of the example of calcium sulphoaluminate cement, calcium sulfate dihydrate (land plaster) and sodium citrate The final setting time of matter polymer cementitious composition is about 60 to about 90 minutes.

Compressive strength

Table 25 shows that is studied in example 8 includes flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate gypsum Powder) and alkali-metal citrate some embodiments of the present invention exploitation geo-polymer cementitious composition compressive strength Behavior.

The case study incorporation calcium sulphoaluminate cement and calcium sulfate (particulate land plaster) and alkali-metal citrate The early stage of the geo-polymer cementitious composition of exploitation to some embodiments of the present invention and the shadow of final compressive strength behavior Ring.By the research, following observation can be drawn：

The compressive strength of the geo-polymer cementitious composition for some embodiments of the present invention studied in the example is at any time Between and continue to increase.

Those compared to the cementitious composition of some embodiments of the present invention comprising calcium sulfate (particulate land plaster) are (mixed Compound 1 to 4), the early stage compressive strength of the blend composition (mixture 1 of example 7) without calcium sulfate and final compression are strong Degree is lower.

The test result of comparative example 7 and example 8, it is observed that the geo-polymer glue of some embodiments of the present invention Early stage (the 4 hours and 24 hours) compressive strength of composition is connect with the increase of the amount of calcium sulfate (particulate land plaster) in material and Increase.

Under high calcium sulfate (particulate land plaster) amount, the geo-polymer cementitious composition of some embodiments of the present invention Early stage (4 hours and 24 hours) compressive strength it is high.Comprising horizontal equal to about 40wt%, about 50wt% and about 60wt% amount Calcium sulfate (particulate land plaster) blend composition have individually about 4 hours compressive strengths more than about 1500psi and Single about 24 hours compressive strengths more than about 4000psi.

4 hours in early days and 24 hours compressive strengths show, when compared to the about 500psi shown in comparative example 2 and 3 and 4 hours of 2000psi and during 24 hours compressive strengths, some embodiments of the present invention can produce significantly larger early stage compression Intensity.

Some implementations of the invention comprising flying dust, calcium sulphoaluminate, calcium sulfate dihydrate (land plaster) and sodium citrate 28 days compressive strengths of all geo-polymer cementitious compositions of example are high, and are more than about 4500psi.Comprising equal to about Some realities of the invention of the horizontal calcium sulfate dihydrate (particulate land plaster) of 40wt%, about about 50wt% and 60wt% amount The cementitious composition for applying example has the single 28 days compressive strengths for being more than about 6000psi.

Example 9

The purpose of the research is mixed in geo-polymer adhesive composition of the research in some embodiments of the present invention Enter the influence of different amounts of calcium sulfate dihydrate (particulate land plaster).

Table 26 shows that the geo-polymer studied in the example is glued the raw material composition of mixture.

The amount of calcium sulphoaluminate cement used is equal to flying dust weight 80wt% in the blend composition of the example.Ground In the blend composition studied carefully, by the calcium sulfate dihydrate in the form of the horizontal addition particulate land plaster of following amount：Calcium sulphoaluminate water 0wt%, 10wt%, 20wt% and 30wt% of the weight of mud (it is 0,8,16 and 24wt% of flying dust).For in the example Water/adhesive material ratio be held constant at 0.25.

The slump and early stage cracking behavior of material

Table 27 shows that is studied in example 9 includes flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate gypsum Powder) and alkali-metal citrate some embodiments of the present invention geo-polymer cementitious composition initial flow behavior and Slump characteristic.

All blend compositions studied are respectively provided with good rheology and slump behavior, as seen in the test that collapses Observe.It is especially noted that under as little as about 0.25 water/adhesive material ratio, can also obtain this good Rheology and slump behavior.

All mixtures containing calcium sulfate dihydrate (particulate land plaster) do not produce any under kilter Cracking.

Shrinkage behavior

Fig. 9 A show the contraction of the geo-polymer cementitious composition for some embodiments of the present invention studied in example 9 Behavior.The main purpose of the research be study incorporation calcium sulphoaluminate cement and particulate calcium sulfate dihydrate (land plaster) and The shadow of the Shrinkage behavior of the geo-polymer cementitious composition of exploitation of the alkali-metal citrate to some embodiments of the present invention Ring.

From raw material is mixed to start to shrink at measurement when about 4 hours forming water paste.About 75 °F/ Under 50%RH while curing materials, measurement Material shrinkage was of about the total duration of 8 weeks.

It can be drawn the following conclusions by the research and Fig. 9 A：

Contraction rod with the comparative example 4 (not having calcium sulfate) of the cracking before the demoulding comprising calcium sulfate two on the contrary, be hydrated The contraction rod of the example 9 of thing (particulate land plaster) is stable, and the not cracking before or after the demoulding.

Compared to about 0.75% of control mixture composition (example 1) only containing flying dust and alkali-metal citrate Maximum collapse, include the sheet of flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate land plaster) and alkali-metal citrate The geo-polymer cementitious composition (example 9) of some embodiments of invention has the maximum collapse less than about 0.07%.

Mixture combination comprising flying dust, calcium sulphoaluminate cement, calcium sulfate (particulate land plaster) and alkali-metal citrate Thing (mixture 2,3 and 4) has the maximum collapse less than about 0.07%, and includes flying dust, calcium sulphoaluminate cement, alkali metal lemon Hydrochlorate, but the maximum collapse of the control mixture 1 not comprising calcium sulfate (land plaster) is high, is about 0.17%.

Heat release and slurry temperature rise behavior

Fig. 9 B show the heat release of the geo-polymer cementitious composition for some embodiments of the present invention studied in example 9 With slurry temperature rise behavior.Include flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate land plaster) and alkali metal citric acid The cementitious composition of the example of salt only shows extremely gentle temperature rise behavior.Moreover, by water/adhesive material ratio by about 0.30 drop As little as about 0.25 (comparing the result from example 7 and 9) did not changed temperature rise behavior with any significant degree.

Gentle heat release and low-temperature-rise in cure stage process in which materials prevent the excessive thermal expansion of material for assistance It is significant with subsequent cracking and destruction.It is related to the side that the material of big thickness is poured into a mould in material is applied with wherein actual field Formula is in use, the aspect becomes even more helpful.The geology polymerization for some embodiments of the present invention studied in the example It is highly advantageous that thing cementitious composition, which is disclosed as in the particular aspects, because they will be produced more in actual field application Low thermal expansion and the resistance to thermal cracking improved.

Setting time

Table 28 shows the solidification of the geo-polymer cementitious composition for some embodiments of the present invention studied in example 9 Time.

All cementitious compositions studied in the example are respectively provided with solidification behavior extremely fast.Compared to only contain flying dust and The final setting time extremely fast of about 15 minutes of the control mixture composition (example 1) of sodium citrate, includes flying dust, sulphur The some embodiments of the present invention of the example of aluminous cement, calcium sulfate dihydrate (particulate land plaster) and sodium citrate The final setting time of geo-polymer cementitious composition is more than about 45 minutes.Compared to containing calcium sulfate dihydrate (gypsum Powder) some embodiments of the present invention mixture 2 to 4, the control mixture #1 without calcium sulfate (land plaster) has obvious Shorter setting time.Extremely short setting time is problematic for some embodiments of the present invention.

Compressive strength

Table 29 shows that is studied in example 9 includes flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate gypsum Powder) and alkali-metal citrate some embodiments of the present invention exploitation geo-polymer cementitious composition compressive strength Behavior.

By the research, following observation can be drawn：

The compressive strength of the geo-polymer cementitious composition of some embodiments of the present invention in the example with the time and Continue to increase.

Compared to the early stage pressure of the cementitious composition (mixture 2 to 4) of some embodiments of the present invention comprising land plaster Contracting intensity and final compressive strength, the early stage compressive strength and most final pressure of the blend composition (mixture 1) without land plaster Contracting intensity is lower.

Early stage (4 hours and 24 hours) compressive strength of the geo-polymer cementitious composition of some embodiments of the present invention Increase with the increase of the amount of calcium sulfate (particulate land plaster) in material.

Calcium sulfate is used in the geo-polymer cementitious composition for some embodiments of the present invention studied in this example In the case of (particulate land plaster), 4 hours compressive strengths of material are more than about 1000psi.In addition, include calcium sulfate (bird's eye gravel Cream powder) mixture 3 and 4 hours compressive strengths of mixture 4 be more than about 1500psi and about 2000psi respectively.By contrast, In the case of in the absence of calcium sulfate dihydrate (land plaster), about 4 hours compressive strengths of material are relatively extremely low, are less than about 400psi (mixture 1).

The water of calcium sulfate two is used in the geo-polymer cementitious composition of some embodiments of the present invention in this example In the case of compound (particulate land plaster), 24 hours compressive strengths of material are more than about 2500psi.In addition, include calcium sulfate two The mixture 3 of hydrate (particulate land plaster) and about 24 hours compressive strengths of mixture 4 are more than about 3500psi.By contrast, In the case of in the absence of land plaster, about 24 hours compressive strengths of material are less than about 1000psi (mixture 1).

4 hours in early days and 24 hours compressive strengths show, when compared to the about 500psi shown in comparative example 2 and 3 and 4 hours of 2000psi and during 24 hours compressive strengths, some embodiments of the present invention can produce significantly larger early stage compression Intensity.

Some implementations of the invention comprising flying dust, calcium sulphoaluminate, calcium sulfate dihydrate (land plaster) and sodium citrate 28 days compressive strengths of all geo-polymer cementitious compositions of example are high, and are more than about 6000psi.

Example 10

The purpose of the research is mixed in geo-polymer adhesive composition of the research in some embodiments of the present invention Enter the influence of different amounts of calcium sulfate dihydrate (particulate land plaster).

Table 30 shows that the geo-polymer studied in the example is glued the raw material composition of mixture.The mixture of the example The amount of calcium sulphoaluminate cement used is equal to the 80wt% of flying dust weight in composition.The water of calcium sulfate two of particulate land plaster form Compound adds in the blend composition studied so that following amount is horizontal：The 40wt% of the weight of calcium sulphoaluminate cement, 50wt%, 60wt% and 80wt%.Calcium sulfate dihydrate is 32,40,48 and 64wt.% of flying dust.For in the example Water/adhesive material ratio is held constant at 0.25.Sand used is QUIKRETE commerical grade fine sand No.1961, and superplasticizer is BASF CASTAMENT FS20。

The slump and early stage cracking behavior of material

Table 31 shows that is studied in example 10 includes flying dust, calcium sulphoaluminate cement, calcium sulfate (particulate land plaster) and alkali The initial flow behavior of the geo-polymer cementitious composition of some embodiments of the present invention of metal citrate and the spy that collapses Property.

All blend compositions studied are respectively provided with good rheology and slump behavior, as seen in the test that collapses Observe.It is especially noted that under as little as about 0.25 water/adhesive material ratio, can also obtain this good Rheology and slump behavior.

All mixtures containing calcium sulfate dihydrate (particulate land plaster) do not produce any under kilter Cracking.

Shrinkage behavior

Figure 10 A show the receipts of the geo-polymer cementitious composition for some embodiments of the present invention studied in example 10 Indention is.

From raw material is mixed to start to shrink at measurement when about 4 hours forming water paste.About 75 °F/ Under 50%RH while curing materials, measurement Material shrinkage was of about the total duration of 8 weeks.

Following important conclusion can be drawn by the research and Figure 10 A：

With even before the demoulding comparative example 4 (not having calcium sulfate) of cracking contraction rod on the contrary, including calcium sulfate two The contraction rod complete stability of the example 10 of hydrate (particulate land plaster), and do not produce any split before or after the demoulding Line.

Compared to about 0.75% of control mixture composition (example 1) only containing flying dust and alkali-metal citrate Maximum collapse, include the sheet of flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate land plaster) and alkali-metal citrate The geo-polymer cementitious composition of some embodiments of invention has the maximum collapse between about 0.08% to about 0.14%.

It is mixed comprising flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate land plaster) and alkali-metal citrate Polymer composition has the maximum collapse between about 0.08% to about 0.14%.By contrast, comprising flying dust, calcium sulphoaluminate water Mud, alkali-metal citrate, but the maximum collapse of the control mixture 1 of the example 9 without calcium sulfate dihydrate (land plaster) It is about 0.17%.

Heat release and slurry temperature rise behavior

Figure 10 B show putting for the geo-polymer cementitious composition for some embodiments of the present invention studied in example 10 Heat and slurry temperature rise behavior.Include flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate land plaster) and alkali metal lemon The cementitious composition of the example of hydrochlorate only shows extremely gentle temperature rise behavior.Moreover, by water/adhesive material ratio by about 0.30 It was reduced to for about 0.25 (comparing the result from example 8 and 10) and temperature rise behavior is not changed with any significant degree.

Gentle heat release in cure stage process in which materials and low-temperature-rise assist to prevent the excessive thermal expansion of material and with Cracking and destruction afterwards.When material by wherein actual field application in be related to big thickness material cast in a manner of in use, institute Stating aspect becomes even more helpful.The geo-polymer cementitious composition for some embodiments of the present invention studied in the example It is highly advantageous to be disclosed as in the particular aspects because they will be produced in actual field application lower thermal expansion and The resistance to thermal cracking improved.

Setting time

Table 32 shows the solidifying of the geo-polymer cementitious composition for some embodiments of the present invention studied in example 10 Gu the time.

All cementitious compositions studied in the example are respectively provided with solidification behavior extremely fast.Compared to only contain flying dust and The final setting time extremely fast of about 15 minutes of the control mixture composition (example 1) of sodium citrate, includes flying dust, sulphur The geo-polymer cementitious composition of some embodiments of the present invention of the example of aluminous cement, land plaster and sodium citrate Final setting time be more than about 50 minutes.Moreover, compared to the mixture 1 to 4 of the example 10 containing land plaster, without gypsum The control mixture 1 of the example 9 of powder has considerably shorter solidification.

Compressive strength

Table 33 shows that is studied in example 10 includes flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate gypsum Powder) and alkali-metal citrate some embodiments of the present invention exploitation geo-polymer cementitious composition compressive strength Behavior.

By the research, following significant observation can be drawn：

The compressive strength of the geo-polymer cementitious composition for some embodiments of the present invention studied in the example is at any time Between and continue to increase.

Early stage (4 hours and 24 hours) compressive strength of the geo-polymer cementitious composition of some embodiments of the present invention Increase with the increase of the amount of calcium sulfate (particulate land plaster) in material.

Make in all four the geo-polymer cementitious compositions for some embodiments of the present invention studied in this example In the case of calcium sulfate dihydrate (particulate land plaster), 4 hours compressive strengths of material are more than about 2000psi.In fact, About 4 hours compressive strengths of the mixture 1 to 3 comprising calcium sulfate dihydrate (particulate land plaster) are more than about 2500psi.Another On the one hand, in the case of in the absence of land plaster, about 4 hours compressive strengths of material are relatively extremely low, less than about 400psi (examples 9 control mixture #1).

Make in all four the geo-polymer cementitious compositions for some embodiments of the present invention studied in this example In the case of calcium sulfate dihydrate (particulate land plaster), 24 hours compressive strengths of material are more than about 4000psi.Another Aspect, in the case of in the absence of calcium sulfate dihydrate (land plaster), about 24 hours compressive strengths of material are relatively extremely low, small In about 1000psi (the control mixture #1 of example 9).

Some embodiments of the present invention comprising flying dust, calcium sulphoaluminate, calcium sulfate (land plaster) and sodium citrate own 28 days compressive strengths of geo-polymer cementitious composition are high again, and are more than about 7000psi.

Example 11

The purpose of the research is mixing not same amount in geo-polymer adhesive composition of the research in the embodiment Alkali-metal citrate influence.

Table 34 shows that the geo-polymer studied in example 11 is glued the raw material composition of mixture.

The amount of calcium sulphoaluminate cement used is equal to the 80wt% of flying dust weight in the blend composition of the example.With etc. In the calcium sulfate dihydrate of the 30wt% of the weight of calcium sulphoaluminate cement amount addition particulate land plaster form.With flying dust 24wt% uses calcium sulfate dihydrate.The alkali-metal citrate of sodium citrate form in the cementitious composition studied with The following horizontal addition of amount：2.00wt%, 1.25wt%, 0.50wt% and 0.00wt% of the weight of total adhesive material.For this Water/adhesive material ratio in research is held constant at 0.275.Sand is QUIKRETE commerical grade fine sand No.1961, and plasticizer is BASF CASTAMENT FS20。

Initial flow behavior, slump and the early stage cracking behavior of material

Table 35 show studied in example 11 comprising flying dust, calcium sulphoaluminate cement, calcium sulfate (particulate land plaster) and not The initial flow behavior of the geo-polymer cementitious composition of the embodiment of the alkali-metal citrate of same amount and slump characteristic.

All blend compositions studied have good flow behavior and big cake diameter, such as institute in the test that collapses It was observed that.It is especially noted that even if when water/adhesive material is than as little as about 0.275, also obtain this big slump and Self-leveling behavior.

Figure 11 A show the photo of the slump cake for the splicing blend composition studied in example 11.In about 2% lemon The slump cake of mixture 1 under sour sodium is without the crackle for representing dimensional instability or unacceptable contraction.On the other hand, The slump cake of mixture 2,3 and 4 respectively containing about 1.25%, 0.5% and 0% sodium citrate produces several micro- when drying Crackle.Therefore, the experiment is shown, the amount of the alkali-metal citrate in composition is decreased below into some amount can increase bag The cracking possibility of geo-polymer cementitious composition containing flying dust, calcium sulphoaluminate and land plaster.

Shrinkage behavior

Figure 11 B show the Shrinkage behavior of the geo-polymer cementitious composition for the embodiment studied in example 11.This grinds The main purpose studied carefully is the geo-polymer splicing group for studying exploitation of the different amounts of alkali-metal citrate to the embodiment The influence of the Shrinkage behavior of compound.

From raw material is mixed to start to shrink at measurement when about 4 hours forming water paste.About 75 °F/ Under 50%RH while curing materials, measurement Material shrinkage was of about the total duration of 8 weeks.

Following important conclusion can be drawn by the research and Figure 11 B：Under the amount of about 2.0% sodium citrate, maximum is measured Shrink minimum, be about 0.06%.The maximum collapse of material can be increased by reducing the amount of sodium citrate.For example, in about 1.25% lemon Under the amount of lemon acid sodium, it is about 0.14% to measure maximum collapse, and under the amount of about 0.5% sodium citrate, measure maximum collapse Increase to about 0.23%.

Compared to about 0.75% of control mixture composition (example 1) only containing flying dust and alkali-metal citrate Maximum collapse, being somebody's turn to do comprising flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate land plaster) and alkali-metal citrate The geo-polymer cementitious composition of embodiment has the maximum collapse of about 0.06% to about 0.24%.

Heat release and slurry temperature rise behavior

Figure 11 C show heat release and the slurry temperature of the geo-polymer cementitious composition for the embodiment studied in example 11 The behavior of liter.Include the reality of flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate land plaster) and alkali-metal citrate The cementitious composition of example only shows extremely gentle temperature rise behavior.Gentle heat release and low temperature in cure stage process in which materials It is significant to rise excessive thermal expansion for preventing material and subsequent cracking and destruction.When material is with wherein actual field application In be related to big thickness material cast mode in use, the aspect becomes even more helpful.The reality studied in the example The geo-polymer cementitious composition for applying example is disclosed as in the particular aspects being highly advantageous, because they are in actual field The resistance to thermal cracking that will be produced lower thermal expansion in and improve.

Setting time

Table 36 shows the setting time of the geo-polymer cementitious composition of the embodiment of example 11.

All cementitious compositions in the example show solidification behavior extremely fast.Final setting time is with lemon The increase of the amount of sour sodium and reduce.For example, blend composition (the mixture 4 containing about 0% and about 0.5% sodium citrate With mixture 3) there is the final setting time of about 2 hours, and the blend composition containing about 2.0% sodium citrate obtains The final setting time of only about 1 hour.

Example 12

The purpose of the research is mixing various amounts in geo-polymer adhesive composition of the research in the embodiment Alkali-metal citrate influence.

Table 37 shows that the geo-polymer studied in the example is glued the raw material composition of mixture.

The amount of calcium sulphoaluminate cement used is equal to the 80wt% of flying dust weight in the blend composition of the example.With etc. The calcium sulfate of 30wt% in the weight of the calcium sulphoaluminate cement and 24wt% equal to flying dust amount addition particulate land plaster form Dihydrate.Sodium citrate is added in the cementitious composition studied with following amount：The weight of total adhesive material 2.00wt%, 3.00wt%, 4.00wt% and 5.00wt%.Sand is QUIKRETE commerical grade fine sand No.1961, superplasticizer For BASF CASTAMENT FS20.

Initial flow behavior, slump and the early stage cracking behavior of material

Table 38 shows that is studied in example 12 includes flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate gypsum Powder) and different amounts of alkali-metal citrate the embodiment geo-polymer cementitious composition initial flow behavior and collapse Fall characteristic.

Even if when water/adhesive material is than as little as about 0.275, all blend compositions studied also have well Self-leveling, flow behavior and big cake diameter, as collapsed what is observed in test.

All slump cakes for the mixture studied in example 12 produce good flow behavior.In addition, containing different amounts of All four blend compositions of sodium citrate produce the slump cake without crackle.This with lower amount of sodium citrate Some produced in the slump cake of the example 11 of cracking form control.

Shrinkage behavior

Figure 12 A show the Shrinkage behavior of the geo-polymer cementitious composition for the embodiment studied in example 12.

From raw material is mixed to start to shrink at measurement when about 4 hours forming water paste.About 75 °F/ Under 50%RH while curing materials, measurement Material shrinkage was of about the total duration of 8 weeks.

It can be drawn the following conclusions by the example and Figure 12 A：Under about 2% and about 3% sodium citrate amount, total contraction is measured It is minimum, it is about 0.06%.The amount of increase sodium citrate can increase the maximum collapse of material.For example, in about 3% sodium citrate Under amount, it is about 0.14% to measure maximum collapse, and under the amount of about 4% sodium citrate, measure maximum collapse and increase to about 0.23%.

The comparison of the contraction test result of example 11 and example 12 shows in one embodiment, alkali metal lemon be present The preferred amounts scope of hydrochlorate, in the range of the preferred amounts, the geology of the embodiment comprising flying dust, calcium sulphoaluminate and calcium sulfate The Material shrinkage of polymer cementitious composition is minimum.In this embodiment the preferred amounts of alkali-metal citrate be about 1% to About 4%, more preferably from about 2% to about 3%.

Heat release and slurry temperature rise behavior

Figure 12 A show the heat release and slurry temperature rise of the geo-polymer cementitious composition for the embodiment studied in example 12 Behavior.Include the example of flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate land plaster) and alkali-metal citrate Cementitious composition show extremely gentle temperature rise behavior.The amount of increase sodium citrate can increase maximum temperature rise, but generally increase It is minimum, and unobvious.In this embodiment, the gentle heat release in cure stage process in which materials and low-temperature-rise are significantly assisted anti- The only excessive thermal expansion of material and subsequent cracking and destruction.It is related to the material of big thickness in material is applied with wherein actual field Expect the mode of cast in use, the aspect is particularly useful.The geo-polymer cementitious composition for the embodiment studied in the example It is highly advantageous that thing, which is disclosed as in the particular aspects, because they will produce lower thermal expansion in actual field application With the resistance to thermal cracking of raising.

Setting time

Table 39 shows the setting time of the geo-polymer cementitious composition for the embodiment studied in example 12.

When the amount of sodium citrate is increased into about 5% not by the final solidification for the blend composition studied by about 2% Between change to significance degree.During the final solidification of four geo-polymer cementitious compositions of the embodiment studied in this example Between be about 60 minutes to about 110 minutes.

Compressive strength

Table 40 shows that is studied in example 12 includes flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate (particulate gypsum Powder) and varying level alkali-metal citrate embodiment exploitation geo-polymer cementitious composition compressive strength row For.

By the research of the embodiment, following significant observation can be drawn：

The compressive strength of the geo-polymer cementitious composition for the embodiment studied in the example continues to increase with the time.

Under the amount for the different sodium citrates studied in this example, each geo-polymer cementitious composition of the embodiment Early stage (4 hours and 24 hours) compressive strength of thing is substantially similar.

It was found that each geo-polymer of the embodiment studied in this example containing different amounts of sodium citrate is glued 4 hours early stages material compressive strength of composition is more than about 2000psi.

It was found that each geo-polymer of the embodiment studied in this example containing different amounts of sodium citrate is glued 24 hours early stages material compressive strength of composition is about 4000psi.

It was found that each geo-polymer of the embodiment studied in this example containing different amounts of sodium citrate is glued 28 days material compressive strengths of composition are more than about 6000psi.

Example 13

The purpose of the research is mixing anhydrous sulphur in geo-polymer adhesive composition of the research in the embodiment The influence of sour calcium (anhydrous gypsum).

Table 41 shows that the geo-polymer in the example is glued the raw material composition of mixture.

The amount of FASTROCK500 calcium sulphoaluminate cement used is equal to flying dust weight in the blend composition of the example 80wt%.In this study anhydrous gypsum used with trade name USG SNOW WHITE board fillers by U.S. Gypsum (United States Gypsum Company) is made.Anhydrous gypsum is in the blend composition studied to measure water as follows Add and add：0wt%, 10wt%, 20wt% and 30wt% of the weight of calcium sulphoaluminate cement.It is anhydrous in terms of the weight of C class flying dusts Gypsum is added with 0,8,16 and 24wt.% level.Added to sodium citrate (the alkali metal lemon of the cementitious composition of the present invention Hydrochlorate) serve as chemical activating agent.Water/adhesive material ratio is held constant at 0.30.

Initial flow behavior, slump and the early stage cracking behavior of material

Table 42 shows that is studied in example 13 includes flying dust, calcium sulphoaluminate cement, anhydrous gypsum and alkali metal citric acid The initial flow behavior of the geo-polymer cementitious composition of the embodiment of salt and slump characteristic.

All blend compositions studied are respectively provided with good Self-leveling, flow behavior and big cake diameter, such as collapse Fall what is observed in test.

Figure 13 A show the photo of the slump cake for the mixture studied in example 13.It is observed that is studied is all Four blend compositions produce good flow behavior.Also observe that, for the mixture #1 without anhydrous gypsum, collapse Cake produces obvious cracking when drying.However, the geo-polymer cementitious composition for the embodiment containing anhydrous gypsum Thing (mixture 2,3 and 4), slump cake does not produce any cracking under excellent condition.Thus, it can be concluded that by anhydrous gypsum Added to the embodiment geo-polymer cementitious composition provide dry when have the size of excellent crack resistance steady Fixed binding agent.

Shrinkage behavior

Figure 13 B show the Shrinkage behavior of the geo-polymer cementitious composition for the embodiment studied in example 13.

Following important conclusion can be drawn by the research and Figure 13 B：

Mix ground of the anhydrous gypsum to the embodiment of the improvement comprising flying dust, calcium sulphoaluminate cement and alkali-metal citrate The crack-resistant property and dimensional stability of matter polymer cementitious composition, which have, to be significantly affected.With pair of the cracking even before the demoulding The contraction rod of ratio 4 (not having calcium sulfate) on the contrary, the contraction rod of the example 13 comprising dead plaster (anhydrous gypsum) is stable, And any crackle is not produced before or after the demoulding.

Compared to about 0.75% of control mixture composition (example 1) only containing flying dust and alkali-metal citrate Maximum collapse, the geo-polymer of the embodiment comprising flying dust, calcium sulphoaluminate cement, anhydrous gypsum and alkali-metal citrate Cementitious composition has the maximum collapse of about 0.05% to about 0.2%.Thus, it can be concluded that by dead plaster (anhydrous stone Cream) it can help to pole added to the cementitious composition comprising flying dust, calcium sulphoaluminate cement and alkali-metal citrate and significantly drop Low Material shrinkage.

The fly ash mixture composition of the anhydrous gypsum of the amount of about 10wt% containing calcium sulphoaluminate cement measures maximum About 0.05% is punctured into, by contrast, there is flying dust and calcium sulphoaluminate cement, but do not have dead plaster (anhydrous gypsum) Mixture 1 is always punctured into about 0.2%.The result shows, nothing is mixed in the geo-polymer cementitious composition of the embodiment H 2 O calcium sulphate (anhydrous gypsum) helps to significantly reduce Material shrinkage.

From raw material is mixed to start to shrink at measurement when about 4 hours forming water paste.About 75 °F/ Under 50%RH while curing materials, measurement Material shrinkage was of about the total duration of 8 weeks.

Heat release and slurry temperature rise behavior

Figure 13 C show the heat release and slurry temperature rise of the geo-polymer cementitious composition for the embodiment studied in example 13 Behavior.The cementitious composition of the example comprising flying dust, calcium sulphoaluminate cement, anhydrous gypsum and alkali-metal citrate is only shown Go out gentle temperature rise behavior.Gentle heat release and low-temperature-rise in cure stage process in which materials are clearly helpful for preventing material Excessive thermal expansion and subsequent cracking and destruction.It is related to the material cast of big thickness in material is applied with wherein actual field Mode is in use, the aspect is particularly helpful.The geo-polymer cementitious composition for the embodiment studied in the example It is highly advantageous that thing, which is disclosed as in the particular aspects, because they will produce lower thermal expansion in actual field application With the resistance to thermal cracking of raising.

Setting time

Table 43 shows the setting time of the geo-polymer cementitious composition for the embodiment studied in example 1.

Compared to about 15 minutes of the control mixture composition (example 1) only containing flying dust and sodium citrate extremely fast Final setting time, the geology of the embodiment of the example comprising flying dust, calcium sulphoaluminate cement, anhydrous gypsum and sodium citrate The final setting time of polymer cementitious composition was more than 40 minutes.Thus, it can be concluded that by calcium sulphoaluminate cement and anhydrous stone The mixture of cream, which is added in the mixture of flying dust and alkali-metal citrate, to be helped to extend material solidification and Temperature measurement, and So that material is more friendly to user.

Compressive strength

Table 44 shows that is studied in example 13 includes flying dust, calcium sulphoaluminate cement, anhydrous gypsum and alkali metal citric acid The compressive strength behavior of the geo-polymer cementitious composition of the exploitation of the embodiment of salt.

By the research, following observation can be drawn：

The compressive strength of the geo-polymer cementitious composition for the embodiment studied in the example continues to increase with the time.

It is mixed without anhydrous gypsum compared to the cementitious composition (mixture 2 to 4) of the embodiment comprising anhydrous gypsum The early stage compressive strength and final compressive strength of polymer composition (mixture 1) are lower.

Early stage (4 hours and 24 hours) compressive strength of the geo-polymer cementitious composition of the embodiment is with material The increase of the amount of anhydrous gypsum and increase.

In the case of anhydrous gypsum being used in the geo-polymer cementitious composition of the embodiment, material compression in 4 hours Intensity is more than about 2000psi.In addition, 4 hours compressive strengths of mixture 3 and mixture 4 comprising anhydrous gypsum are about 3000psi.By contrast, in the case of anhydrous gypsum being not present in blend composition, 4 hours of the material of mixture 1 Compressive strength is less than about 300psi.

In the geo-polymer cementitious composition of the embodiment, compared to land plaster, the use of anhydrous gypsum provides 4 hours higher compressive strengths.The conclusion is proved by the compressive strength test result of comparative example 13 and example 7.

In the case of anhydrous gypsum being used in the geo-polymer cementitious composition of the embodiment, 24 hours materials of early stage Compressive strength is more than about 3000psi.In addition, about 24 hours compressive strengths of mixture 3 and mixture 4 containing anhydrous gypsum point Chao Guoyue not 4000psi and about 5000psi.On the other hand, in the case of anhydrous gypsum being not present in blend composition, About 24 hours compressive strengths of the material of mixture 1 are relatively low, and are less than about 600psi.

All geo-polymer splicing groups of the embodiment comprising flying dust, calcium sulphoaluminate, anhydrous gypsum and sodium citrate 28 days compressive strengths of compound are high again, and are more than about 6000psi.In composition (mixture 3 and the mixture of the embodiment 4) under the amount of higher anhydrous gypsum, compressive strength is more than about 7000psi within 28 days.By contrast, the material without anhydrous gypsum About 28 days compressive strengths for expecting (mixture 1) are only about 4500psi.

Therefore, very it was unexpectedly found that, compared to the calcium sulfate dihydrate institute using more highly dissoluble relatively Those (referring to the examples 7) obtained, the use of insoluble dead plaster (anhydrous gypsum or dead roasting anhydrite) provide more It is fast solidify, excellent compressive strength is advanced the speed, and higher final compressive strength.

Another unexpected feature of embodiments of the invention is the combination of solidification behavior and compressive strength to the present invention The dependence of the type of calcium sulfate used in thing, as shown in the example 13 to 18.

Example 14：Dead plaster (anhydrous gypsum)

The purpose of the research is mixing anhydrous sulphur in geo-polymer adhesive composition of the research in the embodiment The influence of sour calcium (anhydrous gypsum).

Table 45 shows that the geo-polymer studied in the example is glued the raw material composition of mixture.The mixture of the example The amount of calcium sulphoaluminate cement used is equal to the 80wt% of flying dust weight in composition.Dead plaster (anhydrous gypsum) is being ground Added in the blend composition studied carefully so that following amount is horizontal：40wt%, 50wt%, 60wt% of the weight of calcium sulphoaluminate cement and 80wt%.Anhydrous gypsum is used with 32,40, the 48 of C class flying dusts and 64wt.% level.For the water in the research/splicing material Material ratio is held constant at 0.3.

Initial flow behavior, slump and the early stage cracking behavior of material

Table 46 shows that is studied in example 14 includes flying dust, calcium sulphoaluminate cement, anhydrous gypsum and alkali metal citric acid The initial flow behavior of the geo-polymer cementitious composition of the embodiment of salt and slump characteristic.

All blend compositions studied are respectively provided with good Self-leveling, flow behavior and big cake diameter, such as collapse Fall what is observed in test.

All four blend compositions studied in example 14 produce good flow behavior.For containing anhydrous gypsum Mixture, slump cake do not produce any cracking under excellent condition.Therefore, anhydrous gypsum is added to the embodiment Geo-polymer cementitious composition produces the composition of the dimensionally stable when drying with excellent crack resistance.

Shrinkage behavior

Figure 14 A show the Shrinkage behavior of the geo-polymer cementitious composition for the embodiment studied in example 14.

From raw material is mixed to start to shrink at measurement when about 4 hours forming water paste.About 75 °F/ Under 50%RH while curing materials, measurement Material shrinkage was of about the total duration of 8 weeks.

Following important conclusion can be drawn by the research and Figure 14 A：

With even before the demoulding comparative example 4 (not having calcium sulfate) of cracking contraction rod on the contrary, including anhydrous gypsum Example 14 contraction rod it is stable, and do not produce any crackle before or after the demoulding.

Compared to about the 0.75% of the control mixture composition (example 1) that only includes flying dust and alkali-metal citrate Maximum collapse, the geo-polymer of the embodiment comprising flying dust, calcium sulphoaluminate cement, anhydrous gypsum and alkali-metal citrate Cementitious composition has the maximum collapse less than about 0.17%.

The fly ash mixture composition of the anhydrous gypsum of the amount of about 40wt% containing calcium sulphoaluminate cement measures maximum It is punctured into about 0.2%.By contrast, there is flying dust and calcium sulphoaluminate cement but the contrast of the example 13 without anhydrous gypsum mixes Compound 1 is always punctured into about 0.2%.This is shown in incorporation anhydrous gypsum pair in the geo-polymer cementitious composition of the embodiment It is helpful in significantly reducing Material shrinkage.

The amount of anhydrous gypsum is increased above into certain level has the function that the contraction for increasing material.For example, about Under the amount (mixture 2 of example 13) of 10wt% anhydrous gypsum, it is about 0.05% to measure maximum collapse, and about 80wt%'s Under the amount (mixture 4 of example 14) of anhydrous gypsum, the value that maximum collapse increases to about 0.17% is measured.

Compare the contraction test result from example 13 and example 14, the preferred anhydrous stone for make it that Material shrinkage is minimum be present The amount scope of cream.The preferred scope of the anhydrous gypsum calcium sulphoaluminate cement weight more than 0, but be less than or equal to sulphur aluminium The about 40wt.% of the weight of sour calcium cement.

Setting time

Table 47 shows the setting time of the geo-polymer cementitious composition of the embodiment in example 14.

Advantageously, compared to about 15 minutes of the control mixture composition (example 1) only containing flying dust and sodium citrate Final setting time extremely fast, the implementation of the example comprising flying dust, calcium sulphoaluminate cement, anhydrous gypsum and sodium citrate The final setting time of the geo-polymer cementitious composition of example is more than about 40 minutes.

Compressive strength

Table 48 shows that is studied in example 14 includes flying dust, calcium sulphoaluminate cement, anhydrous gypsum and alkali metal citric acid The compressive strength behavior of the geo-polymer cementitious composition of the exploitation of the embodiment of salt.

By the research, following significant observation can be drawn：The geo-polymer splicing group for the embodiment studied in the example The compressive strength of compound continues to increase with the time.

Compared to the mixture (mixture 1 to 4 of example 14) containing anhydrous gypsum, the contrast mixing without anhydrous gypsum The early stage compressive strength and final compressive strength of compositions (control mixture 1 of example 13) are lower.

In the case of anhydrous gypsum being used in the geo-polymer cementitious composition of the embodiment, material compression in 4 hours Intensity is more than about 2000psi.In addition, 4 hours compressive strengths of the mixture 1 of the anhydrous gypsum containing about 40% amount are more than about 3000psi.By contrast, in the case of being free of anhydrous gypsum in control mixture composition, 4 hours compressive strengths of material Relatively extremely low, it is less than about 300psi, such as can be seen that from the control mixture 1 of example 13.

In the geo-polymer cementitious composition of the embodiment, compared to land plaster, the use of anhydrous gypsum provides 4 hours higher compressive strengths.The conclusion is proved by the compressive strength test result of comparative example 14 and example 8.

In the case of anhydrous gypsum being used in the geo-polymer cementitious composition of the embodiment, 24 hours materials of early stage Compressive strength is more than about 4000psi.On the other hand, in the case of being free of anhydrous gypsum in blend composition, material Compressive strength is relatively extremely low within 24 hours, and it is less than about 600psi, as the control mixture 1 of example 13 can be seen that.

All geo-polymer glue of the embodiment comprising flying dust, calcium sulphoaluminate cement, anhydrous gypsum and sodium citrate It is high again to connect 28 days compressive strengths of composition, and is more than about 7000psi.By contrast, the contrast for example 13 mixes Compound #1,28 days compressive strengths of the material without anhydrous gypsum are only about 4500psi.

As in specification as described above, the test of the composition of the example shows, compared to using sulphur in other instances Those of sour calcium dihydrate acquisition, it is anhydrous with the reaction of aluminosilicate mineral material, calcium sulphoaluminate cement and alkali metal activator Gypsum provides solidification, faster material compressive strength faster and advanced the speed, and higher final compressive strength.

Example 15：Calcium sulfate hemihydrate

The purpose of the research is mixing not same amount in geo-polymer adhesive composition of the research in the embodiment Calcium sulfate hemihydrate influence.

Table 49 shows that the geo-polymer studied in the example is glued the raw material composition of mixture.

The amount of calcium sulphoaluminate cement used is equal to the 80wt% of flying dust weight in the blend composition of the example.At this Calcium sulfate hemihydrate used in research is with trade name HYDROCAL C-Base by U.S. Gypsum (United States Gypsum Company) it is made.HYDROCAL C-Base are the α pattern forms of calcium sulfate hemihydrate.Calcium sulfate hemihydrate Added in the blend composition studied so that following amount is horizontal：0wt%, 10wt% of the weight of calcium sulphoaluminate cement, 20wt% and 30wt%.Horizontal 0,8, the 16 and 24wt.% for flying dust of calcium sulfate hemihydrate.Added to the splicing group of the present invention The sodium citrate (alkali-metal citrate) of compound serves as chemical activating agent, rheology modifier and solidification controlling agent.Ground for this Water/adhesive material ratio in studying carefully is held constant at 0.3.Sand used is QUIKRETE commerical grade fine sand No.1961, surpasses plasticising Agent is BASF CASTAMENT FS20.

Initial flow behavior, slump and the early stage cracking behavior of material

Table 50, which is shown in example 15, includes flying dust, calcium sulphoaluminate cement, calcium sulfate hemihydrate and alkali metal lemon The initial flow behavior of the geo-polymer cementitious composition of the embodiment of hydrochlorate and slump characteristic.

All blend compositions studied are respectively provided with good Self-leveling, flow behavior and big cake diameter, such as collapse Fall what is observed in test.

All mixtures have good flow behavior and Self-leveling behavior.Mixture containing calcium sulfate hemihydrate Slump cake does not produce any cracking under excellent condition.Therefore, calcium sulfate hemihydrate is added to and includes calcium sulphoaluminate water The geo-polymer cementitious composition of the embodiment of mud, flying dust and alkali-metal citrate provide dry when have it is excellent Crack resistance dimensionally stable composition.

Shrinkage behavior

Figure 15 A show the Shrinkage behavior of the geo-polymer cementitious composition for the embodiment studied in example 15.

From raw material is mixed to start to shrink at measurement when about 4 hours forming water paste.About 75 °F/ Under 50%RH while curing materials, measurement Material shrinkage was of about the total duration of 8 weeks.

Following important conclusion can be drawn by the research and Figure 15 A：

Contraction rod with the comparative example 4 (not having calcium sulfate) of cracking even before the demoulding is on the contrary, include calcium sulfate half The contraction rod of the example 15 of hydrate is stable, and does not produce any crackle before or after the demoulding.

Compared to about 0.75% of control mixture composition (example 1) only containing flying dust and alkali-metal citrate Maximum collapse, the geology of the embodiment comprising flying dust, calcium sulphoaluminate cement, calcium sulfate hemihydrate and alkali-metal citrate Polymer cementitious composition measures maximum collapse with about 0.08% to about 0.16%.

The survey of the fly ash mixture composition of the calcium sulfate hemihydrate of the amount of about 10wt% containing calcium sulphoaluminate cement It is about 0.08% to obtain maximum collapse.By contrast, there is flying dust and calcium sulphoaluminate cement, but do not have calcium sulfate hemihydrate Control mixture 1 is always punctured into about 0.2%.This display, sulphur is mixed in the geo-polymer cementitious composition of the embodiment Sour calcium semihydrate significantly reduces Material shrinkage.

Heat release and slurry temperature rise behavior

Figure 15 B show heat release and the slurry temperature rise row of the geo-polymer cementitious composition of the embodiment in example 15 For.The cementitious composition of the example comprising flying dust, calcium sulphoaluminate cement, calcium sulfate hemihydrate and alkali-metal citrate is only Show extremely gentle temperature rise behavior.Gentle heat release and low-temperature-rise in cure stage process in which materials help to prevent material Excessive thermal expansion and subsequent cracking and destruction.The material for being related to big thickness in material is applied with wherein actual field is poured into a mould Mode in use, the aspect becomes even more helpful.The geo-polymer for the embodiment studied in the example is glued It is highly advantageous that composition, which is disclosed as in the particular aspects, because they will produce lower heat in actual field application Expansion and the resistance to thermal cracking improved.

Setting time

Table 51 shows the setting time of the geo-polymer cementitious composition of the embodiment in example 15.

Compared to about 15 minutes of the control mixture composition (example 1) only containing flying dust and sodium citrate extremely fast Final setting time, the embodiment of the example comprising flying dust, calcium sulphoaluminate cement, calcium sulfate hemihydrate and sodium citrate Geo-polymer cementitious composition final setting time be more than about 90 minutes.

As in the description as described above, the comparison of the test result of the example and example 13 and the setting time of example 7 It has been shown that, calcium sulfate hemihydrate is unexpectedly than anhydrous gypsum and land plaster more effectively extending containing flying dust, sulphur aluminic acid The setting time of the composition of calcium cement and alkali-metal citrate.

Compressive strength

Table 52 shows the compressive strength behavior of the geo-polymer cementitious composition of the exploitation of the embodiment in example 15.

By the research, following observation can be drawn：

The compressive strength of the geo-polymer cementitious composition of the embodiment continues to increase with the time.

Compared to the cementitious composition (mixture 2 to 4) of the embodiment comprising calcium sulfate hemihydrate, without calcium sulfate The early stage compressive strength and final compressive strength of the blend composition (mixture 1) of semihydrate are lower.

Early stage (about 4 hours and about 24 hours) compressive strength of the geo-polymer cementitious composition of the embodiment is with material The increase of the amount of calcium sulfate hemihydrate in material and increase.

In the case of calcium sulfate hemihydrate being used in the geo-polymer cementitious composition of the embodiment, 4 hours materials Material compressive strength is more than about 1000psi.In addition, 4 hours of mixture 3 and mixture 4 containing calcium sulfate hemihydrate compress Intensity is more than about 3000psi.On the other hand, for the blend composition without calcium sulfate hemihydrate, 4 hours of material Compressive strength is extremely low, i.e., is less than about 300psi for mixture 1.

In the geo-polymer cementitious composition of the embodiment, compared to land plaster, the use of calcium sulfate hemihydrate Provide 4 hours higher compressive strengths.The conclusion passes through the compressive strength test result of comparative example 15 and the compression of example 7 Strength test results and proved.

In the case of calcium sulfate hemihydrate being used in the geo-polymer cementitious composition of the embodiment, about 24 hours Material compressive strength is more than about 3000psi.In addition, include flying dust, calcium sulphoaluminate, anhydrous gypsum containing calcium sulfate hemihydrate With the mixture 3 of the embodiment of sodium citrate and about 24 hours compressive strengths of mixture #4 geo-polymer cementitious compositions More than about 4000psi.By contrast, it is small for the control mixture composition without calcium sulfate hemihydrate, about the 24 of material When compressive strength it is relatively extremely low, be less than about 600psi for mixture 1.

All geo-polymer splicing groups of the embodiment comprising flying dust, calcium sulphoaluminate, anhydrous gypsum and sodium citrate About 28 days compressive strengths of compound are high again, and are more than about 5000psi.In the composition (mixture 3 and mixed of the embodiment Compound 4) in higher calcium sulfate hemihydrate amount under, compressive strength is more than about 7000psi within 28 days.By contrast, find not 28 days compressive strengths of the contrast material (mixture 1) of sulfur acid calcium semihydrate are less than about 4000psi.

Example 16

The purpose of the research is mixing not same amount in geo-polymer adhesive composition of the research in the embodiment Calcium sulfate hemihydrate influence.

Table 53 shows that the geo-polymer studied in the example is glued the raw material composition of mixture.Reuse and be available from The FASTROCK500 board calcium sulphoaluminate cement of CTS cement companies (CTS Cement Company) is as cementation reaction powder Component.The amount of calcium sulphoaluminate cement used is equal to the 80wt% of C class flying dust weight in the blend composition of the example.Sulphur Sour calcium semihydrate (USG HYDROCAL C-Base) is added in the blend composition studied so that following amount is horizontal：Sulphur 40wt%, 50wt%, 60wt% and 80wt% of the weight of aluminous cement.Calcium sulfate hemihydrate is with the 32 of flying dust, 40,48 Used with 64wt.% level.0.3 is held constant at for the water in the research/adhesive material ratio.Sand is QUIKRETE business Grade fine sand No.1961, superplasticizer are BASF CASTAMENT FS20.

Initial flow behavior, slump and the early stage cracking behavior of material

Table 54 shows that is studied in example 16 includes flying dust, calcium sulphoaluminate cement, calcium sulfate hemihydrate and alkali metal The initial flow behavior of the geo-polymer cementitious composition of the embodiment of citrate and slump characteristic.

All blend compositions studied are respectively provided with good Self-leveling, flow behavior and big cake diameter, such as collapse Fall what is observed in test.

Figure 16 A show the photo of the slump cake for the mixture studied in example 16.All mixtures have good stream Dynamic characteristic and Self-leveling behavior.Also observe that, for the mixture 2,3 and 4 containing calcium sulfate hemihydrate, slump cake produces Some micro-cracks.Thus, it can be concluded that calcium sulfate hemihydrate is added to containing calcium sulphoaluminate cement with a large amount level, flown The mixture of ash and alkali-metal citrate provides the cementitious composition when drying with relatively poor resistance to micro-crack.

Shrinkage behavior

Figure 16 B show incorporation calcium sulphoaluminate cement and calcium sulfate hemihydrate and alkali-metal citrate in example The Shrinkage behavior of the geo-polymer cementitious composition for the embodiment studied in 16.

From raw material is mixed to start to shrink at measurement when about 4 hours forming water paste.About 75 °F/ Under 50%RH while curing materials, measurement Material shrinkage was of about the total duration of 8 weeks.

It can be drawn the following conclusions by the research and Figure 16 c：

Compared to about 0.75% of control mixture composition (example 1) only containing flying dust and alkali-metal citrate Maximum collapse is measured, the embodiment comprising flying dust, calcium sulphoaluminate cement, calcium sulfate hemihydrate and alkali-metal citrate Geo-polymer cementitious composition has measures maximum collapse less than about 0.44%.

The amount of increase calcium sulfate hemihydrate can increase the contraction of material.For example, the calcium sulfate half in about 10wt% is hydrated Under the amount (mixture 1 of example 15) of thing, about 0.08% is always punctured into.It is (real in the amount of about 80wt% calcium sulfate hemihydrate The mixture 4 of example 16) under, total contraction pole of material is significantly increased to about 0.44% value.

Compare the contraction test result from example 15 and example 16, it can be concluded that the preferred of Material shrinkage minimum be present The amount scope of calcium sulfate hemihydrate.The preferred scope of calcium sulfate hemihydrate calcium sulphoaluminate cement weight about 0% Less than or equal in the range of the about 40wt% of the weight of calcium sulphoaluminate cement.

Setting time

Table 55 shows the setting time of the geo-polymer cementitious composition of the embodiment in example 16.

All cementitious compositions studied in the example show quick solidification behavior.Compared to only containing flying dust and lemon The final setting time extremely fast of about 15 minutes of the control mixture composition (example 1) of sour sodium, includes flying dust, sulphur aluminic acid The most final set of the geo-polymer cementitious composition of the embodiment of the example of calcium cement, calcium sulfate hemihydrate and sodium citrate Gu the time is about 120 minutes.

Compare the test result and those of example 15 and example 8 of the example, show calcium sulfate hemihydrate than anhydrous stone Cream and land plaster are more effectively extending the blend composition containing flying dust, calcium sulphoaluminate cement and alkali-metal citrate Setting time.

Compared to the setting time (referring to example 7) obtained using calcium sulfate dihydrate, the form as calcium sulfate The use of calcium sulfate hemihydrate provides much longer setting time.As in specification as described above, the result is expectation Outer, because it is well known in the art that calcium sulfate hemihydrate is the material extremely fast solidified.Compared to the use water of calcium sulfate two The embodiment of compound and dead plaster, in some embodiments of the composition of the present invention addition of calcium sulfate hemihydrate carry The setting time extended is supplied.

Compressive strength

Table 56 shows that is studied in example 16 includes flying dust, calcium sulphoaluminate cement, calcium sulfate hemihydrate and alkali metal The compressive strength behavior of the geo-polymer cementitious composition of the exploitation of the embodiment of citrate.

By the research, following significant observation can be drawn：

The compressive strength of the geo-polymer cementitious composition for the embodiment studied in the example continues to increase with the time.

Compared to the cementitious composition (mixture 1 to 4 of example 16) of the embodiment comprising calcium sulfate hemihydrate, no The early stage compressive strength and final compressive strength of the blend composition (mixture 1 of example 15) of sulfur acid calcium semihydrate are equal It is lower.

In the case of calcium sulfate hemihydrate being used in the geo-polymer cementitious composition of the embodiment, 4 hours materials Material compressive strength is more than about 1500psi.In addition, 4 hours of the mixture 1 of the calcium sulfate hemihydrate containing about 40% amount press Contracting intensity is more than about 2500psi.By contrast, for the control mixture composition (example 15 without calcium sulfate hemihydrate Mixture 1), 4 hours compressive strengths of material are relatively extremely low, and it is less than about 300psi.

In the geo-polymer cementitious composition of the embodiment, compared to land plaster, the use of calcium sulfate hemihydrate Provide 4 hours higher compressive strengths.This passes through the compressive strength test result of comparative example 16 and the compressive strength of example 8 Test result and shown.

In the case of calcium sulfate hemihydrate being used in the geo-polymer cementitious composition of the embodiment, about 24 hours Material compressive strength is more than about 4000psi.On the other hand, for the control mixture composition without calcium sulfate hemihydrate (mixture 1 of example 15), about 24 hours compressive strengths of material are relatively low, and it is less than about 600psi.

All geology of the embodiment comprising flying dust, calcium sulphoaluminate cement, calcium sulfate hemihydrate and sodium citrate are gathered 28 days compressive strengths of compound cementitious composition are high, i.e., more than about 7000psi.By contrast, it is hydrated without calcium sulfate half 28 days compressive strengths of the contrast material (mixture 1 of example 15) of thing are less than about 4000psi.

Example 17：Coarse grain calcium sulfate dihydrate

The purpose of the research is mixing coarse grain sulphur in geo-polymer adhesive composition of the research in the embodiment The influence of sour calcium dihydrate.

Table 57 shows that the geo-polymer studied in the example is glued the raw material composition of mixture.The mixture of the example The amount of calcium sulphoaluminate cement used is equal to the 80wt% of C class flying dust weight in composition.Coarse grain calcium sulfate dihydrate is (at this Text is further referred to as thick land plaster) it is made by U.S. Gypsum (United States Gypsum Company), and can be with Trade name USG Ben FranklinAG Coarse Gypsum are obtained.In each blend composition studied, with not Same amount horizontal (0wt%, 10wt%, 20wt% and 30wt% of the weight of FASTROCK500 calcium sulphoaluminate cement) addition is thick Land plaster.In terms of the weight of flying dust, land plaster is added with 0,8,16 and 24wt.% level.Sand used is QUIKRETE Commerical grade fine sand No.1961, superplasticizer are BASF CASTAMENT.

Initial flow behavior, slump and the early stage cracking behavior of material

Table 58, which is shown in example 17, includes flying dust, calcium sulphoaluminate cement, coarse grain land plaster and alkali-metal citrate The embodiment geo-polymer cementitious composition initial flow behavior and slump characteristic.

All blend compositions studied have good flow behavior and big cake diameter, such as institute in the test that collapses It was observed that.

Figure 17 A show the photo of the slump cake of the geo-polymer cementitious composition for the embodiment studied in example 17. Control mixture 1 is free of any calcium sulfate (coarse grain land plaster), and its slump cake produces obvious cracking when drying.It is however, right In the mixture containing coarse grain land plaster, slump cake does not produce any cracking under excellent condition.Therefore, it can be seen that will It is steady that coarse grain land plaster added to the splicing mixture comprising calcium sulphoaluminate cement, flying dust and alkali-metal citrate provides size Fixed geo-polymer cementitious composition, the geo-polymer cementitious composition have during cure stage in material Gentle heat release and low temperature rise, to prevent the excessive thermal expansion of material and subsequent cracking and destruction when drying.

Shrinkage behavior

Figure 17 B show the Shrinkage behavior of the geo-polymer cementitious composition for the embodiment studied in example 17.

From raw material is mixed to start to shrink at measurement when about 4 hours forming water paste.About 75 °F/ Under 50%RH while curing materials, measurement Material shrinkage was of about the total duration of 8 weeks.

Following important conclusion can be drawn by the result and Figure 17 B of the research：

With even before the demoulding comparative example 4 (not having calcium sulfate) of cracking contraction rod on the contrary, including coarse grain gypsum The contraction rod of the example 17 of powder (mixture 2,3 and 4) is stable, and does not produce any crackle before or after the demoulding.

Compared to about 0.75% of control mixture composition (example 1) only containing flying dust and alkali-metal citrate Maximum collapse, the geology polymerization of the embodiment comprising flying dust, calcium sulphoaluminate cement, coarse grain land plaster and alkali-metal citrate Thing cementitious composition has the maximum collapse of about 0.11% to about 0.16%.

Mixture combination comprising flying dust, calcium sulphoaluminate cement, calcium sulfate (coarse grain land plaster) and alkali-metal citrate Thing (mixture 2,3 and 4) has the maximum collapse of about 0.11% to about 0.16%, and includes flying dust, calcium sulphoaluminate cement and alkali Metal citrate, but the maximum collapse of the control mixture 1 not comprising calcium sulfate (land plaster) is about 0.24%.

Increase the overall reduction that the volume production green material of coarse grain land plaster is shunk in the range of studying in this example.For example, Under the amount of about 10wt% coarse grain land plaster, it is about 0.16% to measure maximum collapse, and in about 30wt% coarse grain land plaster Amount under, measure maximum collapse and be reduced to about 0.11%.

Compare the contraction test result from example 7 and example 17, showing to use, there is more fine-grained land plaster to provide Lower contraction.For example, in the case of with coarse grain land plaster of the about 30wt% amount using example 17, maximum collapse is about 0.11%；On the other hand, under about 30wt% identical gypsum powder quantity, in the case of using the particulate land plaster of example 7, Maximum collapse is only about 0.06%.

Heat release and slurry temperature rise behavior

Figure 17 C show the heat release and slurry temperature rise of the geo-polymer cementitious composition for the embodiment studied in example 17 Behavior.The cementitious composition of example 17 comprising flying dust, calcium sulphoaluminate cement, coarse grain land plaster and alkali-metal citrate is only aobvious Extremely gentle temperature rise behavior is shown.In addition, the temperature rise test result of comparative example 17 and example 7, shows compared to using particulate The temperature rise that land plaster is obtained, relatively lower temperature rise is provided using thick land plaster.Temperature in cure stage process in which materials It is clearly helpful for preventing the excessive thermal expansion of material and subsequent cracking and destruction with heat release and low-temperature-rise.When material is with wherein real It is related to the mode of material cast of big thickness in the field application of border in use, the aspect becomes even more helpful.The example It is highly advantageous that the geo-polymer cementitious composition of the embodiment of middle research, which is disclosed as in the particular aspects, because they The resistance to thermal cracking that will be produced lower thermal expansion in actual field application and improve.

Setting time

Table 59 shows the setting time of the geo-polymer cementitious composition of the embodiment in example 17.

All cementitious compositions studied in the example show quick solidification behavior.Compared to only containing flying dust and lemon The final setting time extremely fast of about 15 minutes of the control mixture composition (example 1) of sour sodium, includes flying dust, sulphur aluminic acid During the final solidification of the geo-polymer cementitious composition of the embodiment of the example of calcium cement, coarse grain land plaster and sodium citrate Between be about 60 minutes.

Compressive strength

Table 60 shows that is studied in example 17 includes flying dust, calcium sulphoaluminate cement, coarse grain land plaster and alkali metal lemon The compressive strength behavior of the geo-polymer cementitious composition of the exploitation of the embodiment of hydrochlorate.

By the research, following observation can be drawn：

The compressive strength of the geo-polymer cementitious composition for the embodiment studied in the example continues to increase with the time.

It is mixed without land plaster compared to the cementitious composition (mixture 2 to 4) of the embodiment comprising coarse grain land plaster The early stage compressive strength and final compressive strength of polymer composition (mixture 1) are lower.

Early stage (about 4 hours and about 24 hours) compressive strength of the geo-polymer cementitious composition of the embodiment is with material The increase of the amount of coarse grain land plaster in material and increase.However, the compressions in 4 hours obtained with the increase of coarse grain gypsum powder content are strong The increase of degree is only nominal, and not highly significant.

In the case of coarse grain land plaster being used in the geo-polymer cementitious composition of the embodiment, the early stage 24 of material Hour material compressive strength is more than about 1000psi.

All geo-polymers of the embodiment comprising flying dust, calcium sulphoaluminate, coarse grain land plaster and sodium citrate are glued 28 days compressive strengths of composition are of a relatively high, i.e., more than about 4000psi.In addition, the amount containing about 20wt% and about 30wt% Coarse grain land plaster blend composition (mixture #3 and #4) 28 days compressive strengths it is especially high, it is more than about 5000psi。

The test result of comparative example 17 and example 7, it can be seen that the use of more fine gypsum provides 4 hours and 24 small When material compressive strength faster increase and relatively higher 28 days material compressive strengths.

Example 18：Coarse grain calcium sulfate dihydrate

The purpose of the research is mixing coarse grain calcium sulfate in geo-polymer adhesive composition of the research in the present invention The influence of dihydrate.

Table 61 shows that the geo-polymer studied in the example is glued the raw material composition of mixture.The mixture of the example The amount of calcium sulphoaluminate cement used is equal to the 80wt% of flying dust weight in composition.In each blend composition studied In, horizontal (40wt%, 50wt%, 60wt% and 80wt% of the weight of calcium sulphoaluminate cement) adds rubble cream in different amounts Powder.Land plaster is added with 32,40, the 48 of C class flying dusts and 64wt.% level.Sand used is that QUIKRETE commerical grades are thin Sand No.1961, superplasticizer are BASF CASTAMENT.

Initial flow behavior, slump and the early stage cracking behavior of material

Table 62, which is shown in example 18, includes flying dust, calcium sulphoaluminate cement, coarse grain land plaster and alkali-metal citrate Embodiment geo-polymer cementitious composition initial flow behavior and slump characteristic.

All blend compositions studied have good flow behavior and big cake diameter, such as institute in the test that collapses It was observed that.

The slump cake of all four blend compositions of the example comprising coarse grain land plaster under excellent condition, and Any cracking is not produced.By contrast, the blend composition (control mixture 1 of example 17) without calcium sulfate (land plaster) Extremely significant cracking is produced when drying.Therefore, the incorporation of coarse grain land plaster is included into calcium sulphoaluminate cement, flying dust and alkali metal lemon The splicing mixture of lemon hydrochlorate provides the geo-polymer splicing group of the dimensionally stable when drying with excellent crack-resistant property Compound.

Shrinkage behavior

Figure 18 A show the Shrinkage behavior of the geo-polymer cementitious composition for the embodiment studied in example 18.

From raw material is mixed to start to shrink at measurement when about 4 hours forming water paste.About 75 °F/ Under 50%RH while curing materials, measurement Material shrinkage was of about the total duration of 8 weeks.

Following important conclusion can be drawn by the research and Figure 18 A：

Contraction rod with the comparative example 4 (not having calcium sulfate) of cracking even before the demoulding is on the contrary, (thin comprising calcium sulfate Grain land plaster) example 18 contraction rod it is stable, and do not produced before or after the demoulding and represent that unacceptable size is steady The crackle of qualitative or undesirable contraction.

Compared to about 0.75% of control mixture composition (example 1) only containing flying dust and alkali-metal citrate Maximum collapse, the geology polymerization of the embodiment comprising flying dust, calcium sulphoaluminate cement, coarse grain land plaster and alkali-metal citrate Thing cementitious composition has about 0.09% maximum collapse.Thus, it can be concluded that by coarse grain land plaster be added to comprising flying dust, The cementitious composition of calcium sulphoaluminate cement and alkali-metal citrate contributes to pole to significantly decrease Material shrinkage.

Can be observed to study in this example includes flying dust, calcium sulphoaluminate cement, coarse grain land plaster and alkali metal lemon The geo-polymer cementitious composition of the embodiment of hydrochlorate has about 0.09% maximum collapse.By contrast, there is flying dust With calcium sulphoaluminate cement, but the maximum collapse of control mixture 1 of the example 17 without thick land plaster is about 0.24%.

The amount for increasing thick land plaster in the range of studying in this example does not produce any big change of Material shrinkage behavior. For example, under about 40wt% to about 80wt% coarse grain gypsum powder quantity scope, different mixtures composition measures maximum collapse It is held constant at about 0.09%.

The contraction test result of comparative example 8 (particulate land plaster) and example 18, show to work as makes in blend composition During with horizontal calcium sulfate (the ＞ 50wt.%) of higher amount, coarse grain land plaster more effectively shrinks to reduce overall material.

Heat release and slurry temperature rise behavior

Figure 18 B show the heat release and slurry temperature rise of the geo-polymer cementitious composition for the embodiment studied in example 18 Behavior.The temperature rise test result of comparative example 18 and example 8, show, compared to the temperature rise obtained using particulate land plaster, to make Lower temperature rise is provided with coarse grain land plaster.Gentle heat release and low-temperature-rise in cure stage process in which materials are clearly helpful for Prevent the excessive thermal expansion of material and subsequent cracking and destruction.It is related to big thickness in material is applied with wherein actual field The mode of material cast is in use, the aspect is also helpful.The geo-polymer glue for the embodiment studied in the example Connect composition and be disclosed as in the particular aspects being highly advantageous because they actual field application in will produce it is lower Thermal expansion and the resistance to thermal cracking improved.

Setting time

Table 63 shows the setting time of the geo-polymer cementitious composition of the embodiment in example 18.

Compared to about 15 minutes of the control mixture composition (example 1) only containing flying dust and sodium citrate extremely fast Final setting time, the ground of the embodiment of the example comprising flying dust, calcium sulphoaluminate cement, coarse grain land plaster and sodium citrate The final setting time of matter polymer cementitious composition is about 70 minutes.

Compressive strength

Table 64, which is shown in example 18, includes flying dust, calcium sulphoaluminate cement, coarse grain land plaster and alkali-metal citrate Embodiment exploitation geo-polymer cementitious composition compressive strength behavior.

By the research, following significant observation can be drawn：

The compressive strength of the geo-polymer cementitious composition for the embodiment studied in the example continues to increase with the time.

Compared to the cementitious composition (mixture 2 to 4) of the embodiment comprising coarse grain land plaster, pair without land plaster It is lower than the early stage compressive strength of blend composition (mixture 1) and final compressive strength.

The test result of comparative example 18 and example 8, show that the use of thinner land plaster provides material compression in 4 hours The more rapidly increase of intensity.For example, can be observed, the situation of particulate land plaster is used in the blend composition of example 8 Under, 4 hours material compressive strengths of acquisition are more than about 1500psi (the mixture #1 to #4 of example 8).

In the case where using coarse grain land plaster as the component in the geo-polymer cementitious composition of the embodiment, material 24 hours early stages compressive strength of material is more than about 2000psi.The test result of comparative example 18 and example 8, it can be concluded that thinner The use of land plaster provide the more rapidly increases of 24 hours material compressive strengths.For example, it can be observed, in example 8 In the case of using particulate land plaster in blend composition, 24 hours material compressive strengths of acquisition are (real more than about 4000psi The mixture 1,2 of example 8 and 3).

In this example comprising flying dust, calcium sulphoaluminate cement, coarse grain land plaster and sodium citrate embodiment allly 28 days compressive strengths of matter polymer cementitious composition are less than about 5000psi.The test result of comparative example 18 and example 8, can To find out that the use of calcium sulfate (particulate land plaster) provides 28 days relatively higher material compressive strengths.For example, in example 8 In the case of using calcium sulfate (particulate land plaster) in blend composition, 28 days material compressive strengths of acquisition are more than about 6000psi (mixture 1 to 3 of example 8).

Example 19

The purpose of the research mixed in geopolymer formulation of the research in embodiments of the invention it is different amounts of The influence of high-purity particulate calcium sulfate dihydrate.

Table 65 shows that the geo-polymer studied in the example is glued the raw material composition of mixture.

The amount of calcium sulphoaluminate cement used is equal to the 80wt% of flying dust weight in the blend composition of the example.This grinds Study carefully the middle particulate calcium sulfate dihydrate used and USG companies (USG is come from trade name USG TERRA ALBA F＆P Company).Calcium sulfate dihydrate adds in the blend composition studied so that following amount is horizontal：Calcium sulphoaluminate cement Weight 0wt%, 10wt%, 20wt% and 30wt%.Calcium sulfate dihydrate is with 0,8, the 16 of C class flying dusts and 24wt.% Horizontal addition.0.30 is held constant at for the water in the research/adhesive material ratio.Sand used is QUIKRETE commodity Level fine sand No.1961, superplasticizer is BASF CASTAMENT.

Initial flow behavior, slump and the early stage cracking behavior of material

Table 66, which is shown in example 19, includes flying dust, calcium sulphoaluminate cement, particulate calcium sulfate dihydrate and alkali metal The initial flow behavior of the geo-polymer cementitious composition of the embodiment of citrate and slump characteristic.

All blend compositions studied have good flow behavior and big cake diameter, such as institute in the test that collapses It was observed that.

The slump cake of control mixture #1 without calcium sulfate produces notable cracking when drying.However, for comprising thin The mixture of grain calcium sulfate dihydrate, slump cake do not produce any cracking under excellent condition.Therefore, by particulate sulfuric acid Calcium dihydrate is provided when drying added to the splicing mixture comprising calcium sulphoaluminate cement, flying dust and alkali-metal citrate The composition of dimensionally stable with excellent crack-resistant property.

Shrinkage behavior

Figure 19 A show the Shrinkage behavior of the geo-polymer cementitious composition for the embodiment studied in example 19.

From raw material is mixed to start to shrink at measurement when about 4 hours forming water paste.About 75 °F/ Under 50%RH while curing materials, measurement Material shrinkage was of about the total duration of 8 weeks.

Following important conclusion can be drawn by the research and Figure 19 C：

With even before the demoulding comparative example 4 (not having calcium sulfate dihydrate) of cracking contraction rod on the contrary, comprising The contraction rod complete stability of the example 19 of particulate calcium sulfate dihydrate, and do not produce any split before or after the demoulding Line.

Compared to about 0.75% maximum receipts of the control mixture (example 1) only containing flying dust and alkali-metal citrate Contracting, the geo-polymer glue for the embodiment comprising calcium sulphoaluminate cement and particulate calcium sulfate dihydrate studied in this example Connecing composition has the maximum collapse of about 0.06% to about 0.08%.

The geo-polymer cementitious composition of the embodiment comprising calcium sulphoaluminate cement and particulate calcium sulfate dihydrate (mixture 2,3 and 4) has the maximum collapse of about 0.06% to about 0.08%；On the other hand, there is flying dust and calcium sulphoaluminate Cement, but the maximum collapse of the control mixture 1 without particulate calcium sulfate is relatively high, is about 0.24%.

The amount for increasing particulate calcium sulfate dihydrate in the range of studying in this example produces the drop that overall material shrinks It is low.For example, under the amount of about 10wt% particulate calcium sulfate dihydrate, it is about 0.08% to measure maximum collapse, and about Under the amount of 30wt% particulate calcium sulfate dihydrate, measure maximum collapse and be reduced to about 0.06%.

The comparison of contraction test result from example 7, example 17 and example 19, shows particulate calcium sulfate dihydrate The use of (particulate calcium sulfate dihydrate) provides lower overall shrinkage.For example, in about 30wt% calcium sulfate dihydrate Amount under, using example 17 coarse grain calcium sulfate dihydrate in the case of, maximum collapse be equal to about 0.11%；In the opposing party Face, under the amount of about 30wt% calcium sulfate dihydrate, in the case of using the particulate calcium sulfate dihydrate of example 19, Maximum collapse is only about 0.06%.

Heat release and slurry temperature rise behavior

Figure 19 B show the heat release and slurry temperature rise of the geo-polymer cementitious composition for the embodiment studied in example 19 Behavior.The splicing group of example 19 comprising flying dust, calcium sulphoaluminate cement, particulate calcium sulfate dihydrate and alkali-metal citrate Compound only shows extremely gentle temperature rise behavior.Gentle heat release and low-temperature-rise in cure stage process in which materials substantially help In the excessive thermal expansion and subsequent cracking and destruction that prevent material.It is related to big thickness in material is applied with wherein actual field Material cast mode in use, the aspect is particularly helpful.The geo-polymer for the embodiment studied in the example It is highly advantageous that cementitious composition, which is disclosed as in the particular aspects, because they are lower by generation in actual field application Thermal expansion and improve the resistance to thermal cracking.

Setting time

Table 67 shows the setting time of the geo-polymer cementitious composition of the embodiment in example 19.

All cementitious compositions studied in the example show quick solidification behavior.Compared to only containing flying dust and lemon The final setting time extremely fast of about 15 minutes of the control mixture composition (example 1) of sour sodium, the geology of the embodiment The final setting time of polymer cementitious composition is about 60 minutes to about 90 minutes.

Compressive strength

Table 68 shows that is studied in example 19 includes flying dust, calcium sulphoaluminate cement, particulate calcium sulfate dihydrate and alkali The compressive strength behavior of the geo-polymer cementitious composition of the exploitation of the embodiment of metal citrate.

By the research, following significant observation can be drawn：

The compressive strength of blend composition continues to increase with the time.

Compared to the geo-polymer cementitious composition (mixture 2 of the embodiment comprising particulate calcium sulfate dihydrate To 4), the early stage compressive strength and final compressive strength of the cementitious composition (mixture 1) without particulate calcium sulfate dihydrate It is lower.

Early stage (about 4 hours and about 24 hours) compressive strength of the geo-polymer cementitious composition of the embodiment is with group The increase of the amount of particulate calcium sulfate dihydrate in compound and dramatically increase.The test knot of comparative example 19, example 17 and example 7 Fruit, it can be concluded that the use of particulate calcium sulfate dihydrate provides the more rapidly increase of 4 hours material compressive strengths.

In the case of particulate calcium sulfate dihydrate being used in the geo-polymer cementitious composition of the embodiment, material 24 hours compressive strengths be more than about 2500psi.The test result of comparative example 19, example 17 and example 7, can be concluded that particulate The use of calcium sulfate dihydrate provides the more rapidly increase of early stage material compressive strength.

All geology of the embodiment comprising flying dust, calcium sulphoaluminate, particulate calcium sulfate dihydrate and sodium citrate are gathered 28 days compressive strengths of compound cementitious composition are of a relatively high, and more than 4500psi.In addition, include about 20wt% peace treaties The geo-polymer blend composition (mixture 3 and 4) of the embodiment of the particulate calcium sulfate dihydrate of 30wt% amount 28 days compressive strengths it is high again, it is more than about 5000psi.

Example 20

The purpose of the research is mixing different amounts of height in geo-polymer adhesive composition of the research in the present invention The influence of purity particulate calcium sulfate dihydrate.

Table 69 shows that the geo-polymer studied in the example is glued the raw material composition of mixture.The mixture of the example The amount of calcium sulphoaluminate cement used is equal to the 80wt% of flying dust weight in composition.The particulate calcium sulfate two used in the research Hydrate comes from USG companies (USG Company) with trade name USG Terra Alba F＆P.Calcium sulfate dihydrate is being ground Added in the blend composition studied carefully so that following amount is horizontal：40wt%, 50wt%, 60wt% of the weight of calcium sulphoaluminate cement and 80wt%.Calcium sulfate dihydrate is added with 32,40, the 48 of C class flying dusts and 64wt.% level.Added to the glue of the present invention The sodium citrate for connecing composition serves as chemical activating agent.0.30 is held constant at for the water in the research/adhesive material ratio.Institute Sand is QUIKRETE commerical grade fine sand No.1961, and superplasticizer is BASF CASTAMENT.

Initial flow behavior, slump and the early stage cracking behavior of material

Table 70, which is shown in example 20, includes flying dust, calcium sulphoaluminate cement, particulate calcium sulfate dihydrate and alkali metal The initial flow behavior of the geo-polymer cementitious composition of the embodiment of citrate and slump characteristic.

All blend compositions studied have good flow behavior and big cake diameter, such as institute in the test that collapses It was observed that.It is especially noted that under as little as about 0.3 water/adhesive material ratio, this big slump can be also obtained With Self-leveling behavior.

The slump cake as made from mixture 1-4 is after drying under excellent condition, and do not produce any cracking.Therefore, Particulate calcium sulfate dihydrate is carried added to the splicing mixture comprising calcium sulphoaluminate cement, flying dust and alkali-metal citrate For having the composition of the dimensionally stable of excellent crack-resistant property when drying.

Shrinkage behavior

Figure 20 A show the Shrinkage behavior of the geo-polymer cementitious composition of the embodiment in example 20.

From raw material is mixed to start to shrink at measurement when about 4 hours forming water paste.About 75 °F/ Under 50%RH while curing materials, measurement Material shrinkage was of about the total duration of 8 weeks.It can be drawn by the research and Figure 20 c Following important conclusion：

With even before the demoulding comparative example 4 (not having calcium sulfate dihydrate) of cracking contraction rod on the contrary, comprising The contraction rod of the example 20 of particulate calcium sulfate dihydrate is stable, and does not produce any crackle before or after the demoulding.

About 0.75% compared to control mixture (example 1) only containing flying dust and alkali-metal citrate measures most It is big to shrink, the geology polymerization for the embodiment comprising calcium sulphoaluminate cement and particulate calcium sulfate dihydrate studied in this example Thing cementitious composition measures maximum collapse with about 0.14% to about 0.23%.

Increase the increasing of the volume production green material Shrinkage behavior of particulate calcium sulfate dihydrate in the range of studying in this example Add.For example, under the amount of about 40wt% particulate calcium sulfate dihydrate, it is about 0.14% to measure maximum Material shrinkage.About Under the amount of 80wt% particulate calcium sulfate dihydrate, measure maximum collapse and increase to about 0.23%.

Heat release and slurry temperature rise behavior

Figure 20 B show the heat release and slurry temperature rise of the geo-polymer cementitious composition for the embodiment studied in example 20 Behavior.It is noted that include the reality of flying dust, calcium sulphoaluminate cement, particulate calcium sulfate dihydrate and alkali-metal citrate The cementitious composition of example 20 only shows extremely gentle temperature rise behavior.Gentle heat release in cure stage process in which materials and low Temperature rise is clearly helpful for preventing the excessive thermal expansion of material and subsequent cracking and destruction.When material is with wherein actual field application In be related to big thickness material cast mode in use, the aspect is helpful.The embodiment studied in the example It is highly advantageous that geo-polymer cementitious composition, which is disclosed as in the particular aspects, because they are in actual field application The resistance to thermal cracking that lower thermal expansion will be produced and improved.

Setting time

Table 71 shows the setting time of the geo-polymer cementitious composition of the embodiment in example 20.

All cementitious compositions studied in the example show quick solidification behavior.Compared to only containing flying dust and lemon The final setting time extremely fast of about 15 minutes of the control mixture composition (example 1) of sour sodium, the geology of the embodiment The final setting time of polymer cementitious composition is about 90 to about 120 minutes.

Compressive strength

Table 72 shows that is studied in example 20 includes flying dust, calcium sulphoaluminate cement, particulate calcium sulfate dihydrate and alkali The compressive strength behavior of the geo-polymer cementitious composition of the exploitation of the embodiment of metal citrate.

By the research, following significant observation can be drawn：

The compressive strength for the blend composition studied continues to increase with the time.

The geo-polymer cementitious composition for the embodiment comprising particulate calcium sulfate dihydrate studied in the example Early stage (about 4 hours and about 24 hours after the mixing) compressive strength of (mixture 1 to 4), which is noticeably greater than, is free of particulate calcium sulfate two Early stage (about 4 hours and about 24 hours after mixing) pressure of the control mixture composition (mixture 1 of example 19) of hydrate Contracting intensity.

Early stage/early stage (after mixing 4 hours and 24 hours) of the geo-polymer cementitious composition of the embodiment Compressive strength is high, and keeps fairly constant with the increase of the amount of particulate calcium sulfate dihydrate in composition.

The test result of comparative example 20 and example 18, it is clear that the use of particulate calcium sulfate dihydrate provides 4 The more rapidly increase of hour material compressive strength.For example, can be observed, particulate is used in the blend composition of the example In the case of calcium sulfate dihydrate, 4 hours material compressive strengths of acquisition more than about 2000psi (mixture 1 of example 20 to 3).Compared to effect, 4 hours compressive strengths of the blend composition comprising the horizontal coarse grain land plaster of equal amount are less than about 600psi, such as it can be seen that by the mixture 1 to 3 of example 18.

In the case of using particulate calcium sulfate dihydrate, the geo-polymer for the embodiment studied in this example 24 hours compressive strengths of cementitious composition are more than about 3500psi.The water of particulate calcium sulfate two in the blend composition of example 20 The use of compound provides 24 hours material compressive strengths (mixture 1 to 4 of example 20) more than about 3500psi；And for The mixture #1 to 4 of example 18, the blend composition containing the horizontal coarse grain land plaster of equal amount, which provides, to be less than about 2500psi 24 hours compressive strengths.

That studies in this example includes the implementation of flying dust, calcium sulphoaluminate, particulate calcium sulfate dihydrate and sodium citrate 28 days compressive strengths of the geo-polymer cementitious composition of example are greater than about 5000psi.In addition, the mixture #1 for example 20 To 3, about 28 days compressive strengths of material are more than about 6000psi.The comparison of the test result of example 20 and example 18 shows, particulate The use of calcium sulfate dihydrate provides about 28 days relatively higher material compressive strengths.For example, in the mixture of example 20 In the case of using particulate calcium sulfate dihydrate in composition, the about 28 days materials compression obtained more than about 7,000psi is strong Degree.

Example 21

The low amounts (about 20 parts by weight of flying dust) that case study incorporation is combined with calcium sulfate and alkali-metal citrate Calcium sulphoaluminate cement influence.

Table 73 shows that the geo-polymer studied in the example is glued the raw material composition of mixture.Using being available from CTS The FASTROCK500 board calcium sulphoaluminate cement of cement company (CTS Cement Company) is as the cementation reaction in the research The component of property powder.The amount of aluminous cement used is equal to 0,5,10, the 15 of C class flying dusts in the blend composition of the example And 20wt%.The particulate calcium sulfate dihydrate (herein referred as land plaster) used in this study is by U.S. Gypsum (United States Gypsum Company) is made.In each blend composition studied, land plaster is with sulphur aluminium The 50% amount addition of the weight of sour calcium cement.Land plaster is added with the 0 of flying dust, 2.5,5,7.5 and 10wt.% level.Institute Sand is QUIKRETE commerical grade fine sand No.1961, and superplasticizer is BASF CASTAMENT.It is available from air products public affairs The SURFYNOL500S surfactants of department (Air Products, Inc.) also serve as defoamer and wetting agent.

Initial flow behavior, slump and the early stage cracking of material

Table 74 shows that is studied in example 21 includes flying dust, calcium sulphoaluminate cement, calcium sulfate (particulate land plaster) and alkali The initial flow behavior of the geo-polymer cementitious composition of the embodiment of metal citrate and slump characteristic.

All blend compositions (mixture 2 to 5) of the embodiment are respectively provided with good Self-leveling, flow behavior and big Cake diameter, as collapse test what is observed in.It is especially noted that even in about 0.275 extremely low water/splicing Under material ratio, this big slump and Self-leveling behavior can be also obtained.For standard Portland cement base or gypsum base material, only when Water/adhesive material ratio can just obtain this flowing property and Self-leveling behavior when being more than about 0.45.

The slump cake of the blend composition (mixture 2 to mixture 5) of the embodiment of the example does not produce when drying Raw any cracking.Thus, it can be concluded that even if with low amount (the about 20wt% of flying dust weight) by calcium sulphoaluminate cement and sulfuric acid Splicing mixture of calcium dihydrate (particulate land plaster) incorporation comprising flying dust and alkali-metal citrate, also providing has The geo-polymer cementitious composition of the dimensionally stable of excellent crack resistance when drying.

Shrinkage behavior

Figure 21 A show the Shrinkage behavior of the geo-polymer cementitious composition for the embodiment studied in example 21.For Mixture 2 is to mixture 5, from raw material is mixed to start to shrink at measurement when about 4 hours forming water paste.It is right In control mixture 1, because excess material is shunk, shrink rod within 4 hours and rupture in a mold, as can be seen that in Figure 21 B.Contrast Contraction data shown in Figure 21 A of mixture 1 is shown (shrank test in the same period to start) demoulding when about 1 hour Rod pole early stage Material shrinkage behavior.Figure 21 C are shown (shrank measurement to start simultaneously at) all of the demoulding when 1 hour The Material shrinkage of the pole early stage of five mixtures.Under about 75 °F/50%RH while curing materials, measurement Material shrinkage of about The total duration of 8 weeks.

Following important conclusion can be drawn by the research and Figure 21 A and 21B：

Calcium sulphoaluminate cement is even if with minimum amount (the about 20wt% of flying dust weight) incorporation also to improving comprising flying dust, sulphur The dimensional stability of the geo-polymer cementitious composition of the embodiment of sour calcium dihydrate and alkali-metal citrate and with Crack resistance afterwards, which has, to be significantly affected.With even cracking is free of calcium sulphoaluminate cement and particulate calcium sulfate two before the demoulding Rod is shunk on the contrary, including calcium sulphoaluminate cement and the water of particulate calcium sulfate two in 4 hours of the control mixture 1 of hydrate (land plaster) The contraction rod of the mixture 2 of compound (land plaster) to mixture 5 is stable, and the not cracking before or after the demoulding.

Compared to being more than about for mixture (control mixture 1 of example 21) for only including flying dust and alkali-metal citrate 0.5% maximum collapse, include flying dust, calcium sulphoaluminate cement, particulate calcium sulfate dihydrate (land plaster) and alkali metal lemon The geo-polymer cementitious composition of the embodiment of hydrochlorate has the maximum collapse less than about 0.10%.It is worth noting that, It is only about 0.07% that the dominant record of mixture 2 comprising 5 parts of calcium sulphoaluminate cement, which shrinks, and includes about 10 parts of calcium sulphoaluminate water It is only about 0.05% that the dominant record of the mixture 3 of mud, which shrinks,.Therefore, even if by a small amount of calcium sulphoaluminate cement and particulate sulfuric acid Calcium dihydrate (land plaster) also contributes to pole significantly added to the cementitious composition comprising flying dust and alkali-metal citrate Reduce Material shrinkage.

Heat release and slurry temperature rise behavior

Figure 21 D show the heat release and slurry temperature rise of the geo-polymer cementitious composition for the embodiment studied in example 21 Behavior.Include the example 21 of flying dust, calcium sulphoaluminate cement, particulate calcium sulfate dihydrate (land plaster) and alkali-metal citrate Cementitious composition only show extremely gentle temperature rise behavior.Gentle heat release and low-temperature-rise in cure stage process in which materials It is clearly helpful for preventing the excessive thermal expansion of material and subsequent cracking and destruction.Related in material is applied with wherein actual field And the mode of the material cast of big thickness is in use, the aspect is helpful.The geology for the embodiment studied in the example Polymer cementitious composition is highly advantageous in the particular aspects, because they are lower by generation in actual field application Thermal expansion and improve the resistance to thermal cracking.

Setting time

Table 75 shows the setting time of the geo-polymer cementitious composition of the embodiment in example 21.

All cementitious compositions studied in the example show solidification behavior extremely fast, final setting time be about 45 to About 60 minutes.Also observe that, compared to only include flying dust and alkali-metal citrate contrast cementitious composition (example 21 Mixture 1), being somebody's turn to do comprising flying dust, calcium sulphoaluminate cement, particulate calcium sulfate dihydrate (land plaster) and alkali-metal citrate The cementitious composition of the exploitation of embodiment has relatively longer setting time (initial solidification time and final setting time two Person).

Compressive strength

Table 76, which is shown in example 21, includes flying dust, calcium sulphoaluminate cement, particulate calcium sulfate dihydrate (land plaster) With the compressive strength behavior of the geo-polymer cementitious composition of the exploitation of the embodiment of alkali-metal citrate.

By the research, following observation can be drawn：

The compressive strength of the geo-polymer cementitious composition for the embodiment studied in the example continues to increase with the time.

It polymerize using the geology of calcium sulphoaluminate cement and particulate calcium sulfate dihydrate (land plaster) as the embodiment In the case of the component of thing cementitious composition, 4 hours early stages compressive strength of material is more than about 1000psi.

Using the geology of calcium sulphoaluminate cement and particulate calcium sulfate dihydrate (land plaster) as the embodiment research In the case of the component of polymer cementitious composition, 24 hours early stages compressive strength of material is more than about 2000psi.

About 28 days compressive strengths of all geo-polymer cementitious compositions for the embodiment studied in the example exceed About 4000psi.

Example 22

The case study using alkali metal hydroxide (sodium hydroxide) or alkali metal hydroxide (sodium hydroxide) and The mixture activation of sour (citric acid) comprising flying dust, calcium sulphoaluminate cement, particulate calcium sulfate the embodiment exploitation ground The physical property of matter polymer cementitious composition.

Table 77 shows that the geo-polymer studied in the example is glued the raw material composition of mixture.The mixture of the example The amount of calcium sulphoaluminate cement used is equal to the 20wt% of flying dust weight in composition.In each blend composition studied In, land plaster is added with the 10wt.% of 50%, the C class flying dusts of the weight of calcium sulphoaluminate cement amount.By sodium hydroxide and lemon The mixture of acid is added in the cementitious composition of the present invention to serve as chemical activating agent.Two in the mixture studied (mixture 2 and mixture 3) only contains sodium hydroxide as chemical activating agent, and is free of citric acid.Similarly, in mixture One (mixture 1) only contains citric acid for chemical activation, without containing sodium hydroxide.It is available from Air Products Company (Air Products, Inc.) SURFYNOL500S surfactants be used as defoamer and wetting agent.Sand is QUIKRETE commerical grades Fine sand No.1961, superplasticizer are BASF CASTAMENT FS20.

Initial flow behavior and slump

Table 78 show the geo-polymer cementitious composition for the embodiment studied in example 22 initial flow behavior and Slump characteristic.

For the mixture 1 containing citric acid but without sodium hydroxide, it is noted that mixing material is extremely hard, and complete in mixing It is complete non-machinable.On the other hand, the blending containing sodium hydroxide (mixture 2 and mixture 3) or sodium hydroxide and citric acid The blend composition of thing (mixture 4 and mixture 5) is easy to process, and also such as they are straight with respect to bigger cake in the test that collapses Shown in footpath.It is especially noted that under about 0.275 extremely low water/adhesive material ratio, can also obtain this good Processability.For standard Portland cement base or gypsum base material, only can just be obtained when water/adhesive material ratio is more than about 0.45 Obtain this flowing property and Self-leveling behavior.

Shrinkage behavior

Figure 22 A show the Shrinkage behavior of the geo-polymer cementitious composition in example 22.

From raw material is mixed to start to shrink at measurement when about 4 hours forming water paste.About 75 °F/ Under 50%RH while curing materials, measurement Material shrinkage was of about the total duration of 8 weeks.

Following important conclusion can be drawn by the research and Figure 22 A：

It is only about small as blend composition (the mixture 2 and mixture 3) display of chemical activating agent comprising sodium hydroxide In about 0.1% extremely low contraction.It is worth noting that, the maximum collapse of the mixture 2 only containing 1% sodium hydroxide is less than about 0.05%.For the mixture 3 of the sodium hydroxide of the amount containing about 3%, maximum collapse increases to about 0.09%.

Cementitious composition (mixing of the mixture comprising sodium hydroxide and citric acid as the embodiment of chemical activating agent Thing 4 and mixture 5) display that extremely low contraction.Containing citric acid and the mixture 3 of about 1% sodium hydroxide maximum collapse Only about 0.05%.For containing citric acid and the sodium hydroxide of about 3% amount mixture 5, maximum collapse increases to about 0.25%.

Heat release and slurry temperature rise behavior

Figure 22 B show the heat release and slurry temperature rise behavior of the geo-polymer cementitious composition in example 22.The example In cementitious composition (mixture 2 to mixture 5) show extremely low temperature increase.Only with citric acid (no sodium hydroxide) Mixture 1 hardens in mixing, and shows the reactivity of extreme difference, as shown in extremely low temperature rise.The material during cure stage Gentle heat release and low-temperature-rise in material are clearly helpful for preventing the excessive thermal expansion of material and subsequent cracking and destruction.Work as material In use, the aspect is helpful in a manner of being related to the material cast of big thickness in the application of wherein actual field.The reality The geo-polymer cementitious composition for the embodiment studied in example is disclosed as in the particular aspects being highly advantageous, because it Lower thermal expansion and the resistance to thermal cracking improved will be produced in actual field application.

Setting time

Table 79 shows the setting time of the geo-polymer cementitious composition in example 22.

All cementitious compositions (mixture 2 to mixture 5) for the embodiment studied in the example show pole Quick solidification behavior, and final setting time is about 15 to about 60 minutes.Compared to the sodium hydroxide of amount comprising about 3% Blend composition (i.e. mixture 3 and mixture 4), the blend composition comprising the horizontal sodium hydroxide of about 1% amount are (mixed Compound 2 and mixture 4) there is relatively longer setting time (and open hour).For some applications, extremely short setting time It is problematic, because short material working life (working life) causes to process the material quickly solidified in actual field is applied Obvious difficulty.

Compressive strength

Table 80, which is shown in example 22, includes flying dust, calcium sulphoaluminate cement, calcium sulfate (particulate land plaster) and alkali metal The compressive strength behavior of the geo-polymer cementitious composition of the exploitation of the embodiment of chemical activating agent.

By the research, following significant observation can be drawn：

The compressive strength of the geo-polymer cementitious composition for the embodiment studied in the example continues to increase with the time.

Calcium sulphoaluminate cement and land plaster are being used as the component in the geo-polymer cementitious composition of the embodiment In the case of, 4 hours early stages compressive strength of material is more than about 1000psi.When sodium hydroxide itself serves as chemical activating agent (the mixture 2 and mixture 3) or (mixture 4 and mixed when the mixture of sodium hydroxide and citric acid is used as chemical activating agent Compound 5) it is exactly such.

Calcium sulphoaluminate cement and land plaster are being used as in the geo-polymer cementitious composition of the research of the embodiment Component in the case of, 24 hours early stages compressive strength of material is more than about 2000psi.When sodium hydroxide itself serves as chemical work (mixture 2 and mixture 3) or (mixture when the mixture of sodium hydroxide and citric acid is used as chemical activating agent during agent 4 and mixture 5) be exactly such.

28 days compressive strengths of all geo-polymer cementitious compositions for the embodiment studied in the example are more than about 5000psi.When sodium hydroxide itself serves as chemical activating agent (mixture 2 and mixture 3) or when sodium hydroxide and lemon The mixture of acid is used as such again during chemical activating agent (mixture 4 and mixture 5).

Example 23

This example shows incorporation not same amount (20 parts by weight, 40 parts by weight, 60 parts by weight and 80 parts by weight of flying dust) Calcium sulphoaluminate cement and with the 6 of flying dust, 12, the 18 and 24wt.% horizontal calcium sulfate dihydrate added to the present invention's The influence of the Shrinkage behavior of the pole early stage of geo-polymer cementitious composition.The composition of test is listed in table 81.Sand is QUIKRETE commerical grade fine sand No.1961, superplasticizer are BASF CASTAMENT FS20.

The Shrinkage behavior of pole early stage

Figure 23 A show the contraction row of the pole early stage of the geo-polymer cementitious composition for the embodiment studied in example 23 For.

Pole early-age shrinkage test such as [0277] section progress, but when raw material is mixed to form water paste from Start initial measurement when about 1 hour.The main purpose of the research, which is to study, mixes different amounts of calcium sulphoaluminate cement (flying dust About 20 to about 80 parts by weight) and particulate calcium sulfate dihydrate to the extremely early of the geo-polymer cementitious composition of the embodiment The influence of phase Shrinkage behavior.

By Figure 23 A and table 82 it is observed that the magnitude of pole early-age shrinkage is with sulphur aluminic acid in the composition of the embodiment The increase of the amount of calcium cement and increase.This is very unexpected result.

Table 82 summarizes the shrinking percentage using rod made from the mixture in example 23 as shown in fig. 23 a.

Aforementioned result illustrates the epochmaking aspect of the present invention.These results are very unexpected, and are shown The pole early-age shrinkage of the cementitious composition of the increased embodiment with the increased amount of the calcium sulphoaluminate cement in composition. These results indicate that if the main purpose of application is to make the pole early-age shrinkage of material and the magnitude always shunk reaches minimum, It is advantageously that the amount holding of the calcium sulphoaluminate cement in the composition of the embodiment and related embodiment is relatively low (preferably from about 20 parts or lower).Although the reason for not understanding the pole early-age shrinkage for the material observed herein completely, it is believed that early-age shrinkage is returned Because in coming from the self-desiccation of reactant materials and the chemistry of stereomutation and autogenous shrinkage.

The amount of calcium sulphoaluminate cement in the composition of the embodiment and related embodiment and calcium sulfate is kept relatively low Another principal benefits are to significantly reduce the possibility of weathering.Asked it should be noted that the high rate of decay in material not only produces aesthetics Topic, it can also cause material damage and damage due to expansion reaction and in the later stage, and the expansion reaction can be due to being present in through hard The chemistry and hydration reaction of salt in the material of change and occur.

The amount of calcium sulphoaluminate cement in the composition of the embodiment and calcium sulfate is kept into relatively low another principal benefits It is the cost for significantly reducing raw material.

Example 24

This example shows flying dust, calcium sulphoaluminate cement, particulate calcium sulfate dihydrate (i.e. gypsum or land plaster) and alkali The tensile bond strength performance of metal salt.Four blend compositions are studied altogether.

In table 83, mixture 1 represents the geo-polymer glue of the invention without film forming redispersible polymer powder Connect composition.On the other hand, mixture 2 to mixture 4 represents that the film forming containing horizontal addition in different amounts is redispersible The geo-polymer cementitious composition of the invention of polymer powder.Use is by watt gram poly- in last three blend compositions Trade name VINNAPAS5025L film forming redispersible polymer powder made from compound company (WACKER Polymers) (vinyl acetate/ethylene copolymer).Use Quickrete commerical grade fine sand No.1961 and BASF CASTAMENT FS20 Superplasticizer and the SURFYNOL500S defoamers for being available from Air Products Company (Air Products, Inc.).

Tensile bond strength

Stretching between the geo-polymer cementitious composition referred in research Portland cement base mortar base material and table 102 Adhesion strength.The cube mold of about 2 inches of x2 inch x2 inches is filled into half first by Portland cement base mortar Thickness (1 ").After casting, material is made to solidify in sealed plastic bag and harden at least about 28 days.Solidify at about 28 days Into afterwards, primed using top surface of the acrylic primer in Portland cement mortar.Then, by the embodiment according to table 84 Geo-polymer cementitious composition be poured into mould until top surface.The top surface of newly-installed material is floating flat to produce Surface.Then sample solidification is made until when test.After solidification is completed, test sample is stripped, will about 2 inches of x2 English Very little steel anchor block epoxy resin is bonded to top surface and the bottom surface of sample.Then in suitable test frame (MTS test machines) with Pulling force pulls sample, records final breaking load.Pass through breaking load divided by Portland cement mortar base material and geo-polymer Bonding surface between adhesive material is long-pending and calculates bursting stress.For each mixture studied in the example, five are tested Sample is until destroy.

Table 84 shows the average tensile adhesion strength for the four geo-polymer blend compositions studied in the example. All samples solidify 8 days, and test tensile bond strength.It is observed that all four blend compositions studied are equal With high tensile bond strength.It is especially noted that for all four of the invention studied in this example Geo-polymer cementitious composition, tensile bond strength are more than about 200psi.

The stretch-bonded of geo-polymer cementitious composition (mixture 1) without any redispersible polymer powder is strong Spend high, about 298psi.This is very unexpected result, because commercially available using other in the case of in the absence of polymer Portland cement sill and product generally unavailable so high tensile bond strength.It should be noted that by redispersible polymer Powder (mixture 2 to 4) does not produce any of tensile bond strength added to the geo-polymer cementitious composition of the embodiment Significantly change or increase.The result illustrates a very important aspect of the composition of the present invention, i.e., for increasing the reality Tensile bond strength of the geo-polymer cementitious composition to other base materials of example is applied, redispersible polymer powder is in the implementation It is not required in the geo-polymer cementitious composition of example.When material is used to be bonded in the repairing application of other base materials, Tensile bond strength is very useful property.Cohesive quality finally determines repairing work in short term and long-term durability and persistently Property.It can cause leafing, cracking and other failure modes with the poor bonding of base material.

Aforementioned result represents the epochmaking aspect of the present invention, because the result is shown, makes us full to obtain The adhesion strength performance of meaning, the polymer of costliness is optionally removed from the geopolymer formulation of the embodiment.This makes The geo-polymer cementitious composition for obtaining the embodiment is repaiied relative to other commercially available splicing based on other inorganic binder technologies It is extremely competitive in unique and cost to mend product.

Using containing other kinds of redispersible polymer powder (such as acrylic compounds, styrene-acrylic copolymer, SB and other) the geopolymer formulation of the embodiment carry out other tensile bond strength Test.The tensile bond strength result of these compositions is high, and similar to the result as above reported in this example.

Example 25

This example shows the reality for including flying dust, calcium sulphoaluminate cement, particulate anhydrous gypsum and alkali-metal citrate Apply the physical property of the geo-polymer cementitious composition of the exploitation of example.One main purpose of the research be study incorporation≤ Geo-polymer group of the calcium sulphoaluminate cement and particulate anhydrous gypsum of the low amounts of about 40 parts by weight of flying dust to the embodiment The influence of the compressive strength behavior of compound.

The amount of calcium sulphoaluminate cement used is equal to 5,10,20, the 30 of flying dust weight in the blend composition of the example And 40wt%.USG SNOW WHITE fillers are used in the research, it is a kind of particulate dead plaster (anhydrous gypsum).Institute In each blend composition of research, SNOW WHITE fillers are added with 50% amount of the weight of calcium sulphoaluminate cement.Nothing Water gypsum is added with 2.5,5,10, the 15 of C class flying dusts and 20wt% level.QUIKRETE commerical grade fine sands No.1961, BASF CASTAMENT FS20 superplasticizers, the SURFYNOL500S defoamings from Air Products Company (Air Products, Inc.) Agent and wetting agent and it is available from AXILATs of the Mai Tute with chemical company (Momentive Specialty Chemicals) RH200XP succinoglycan hydrocolloids.Table 85 shows the composition tested in the example.

Compressive strength and setting time

Table 86 shows that is studied in example 25 includes flying dust, calcium sulphoaluminate cement, particulate anhydrous gypsum and alkali metal lemon The compressive strength behavior of the geo-polymer cementitious composition of the exploitation of the embodiment of lemon hydrochlorate.

Compared to the analogous composition (institute's protrusion in example as before) containing calcium sulfate dihydrate, as obtained in the example The compressive strength of the geo-polymer cementitious composition of the embodiment comprising anhydrous gypsum obtained is significantly larger.This illustrates to compare In calcium sulfate dihydrate described in the description of the invention, using insoluble dead plaster, (anhydrous gypsum is dead Burn anhydrous gypsum) unexpected benefit.

Mixture #1 and mixture #2 for containing calcium sulphoaluminate cement and anhydrous gypsum with lower amount, the morning of material 4 hours phases compressive strength is more than about 1500psi, the mixture for containing calcium sulphoaluminate cement and anhydrous gypsum with higher amount 3 to 5,4 hours early stages compressive strength of material is more than about 3000psi.

Mixture 1 and mixture 2 for containing calcium sulphoaluminate cement and anhydrous gypsum with lower amount, the early stage of material Compressive strength is more than about 2000psi within 24 hours, the mixture 3 for containing calcium sulphoaluminate cement and anhydrous gypsum with higher amount To 5,4 hours early stages compressive strength of material is more than about 5000psi.

All geo-polymer glue for the embodiment containing calcium sulphoaluminate cement and anhydrous gypsum studied in the example 28 days compressive strengths for connecing composition are more than about 7000psi.

It is further noted that (dashed forward compared to the analogous composition containing calcium sulfate dihydrate in example as before Go out), the geo-polymer cementitious composition of the obtained embodiment comprising anhydrous gypsum relatively faster solidifies.In the example Between the final setting time of five blend compositions of research is about 25 to about 35 minutes.

The geo-polymer cementitious composition of the invention containing anhydrous gypsum as prominent in this example is quick wherein It is particularly useful that solidification and rapid strength, which increase in the application for exclusive requirement,.

Example 26

The example shows, geo-polymer cementitious composition of the invention particularly useful as multiple base materials (such as concrete, Timber etc.) on Self-leveling floor lining.Especially, the composition similar with the composition being described in the example is highly available for Make the existing concrete smooth surface of coarse non-flat forms and flatten.

Table 87 shows to produce the combination of materials of the embodiment used on existing concrete plate of smooth surface Thing.

The area of the size of the concrete slab of its upper geo-polymer top material is about 22 feet of English of x about 11.5 Chi.The surface of cleaning board first, to remove the dust and chip that are adhered to plate surface.Then will using acrylic compounds bottom plate priming paint Plate surface is primed.Use material of the hand drill blender in drum shown in mixture table 87.Using hand drill blender in mixing drum In mix the sizing material (size) that two batches refer in table 26 immediately.Water is poured into mixing drum first, dry powder is added afterwards and is total to Mixed thing.Material incorporation time is about 2 to about 3 minutes, to obtain the geo-polymer slurry without caking of the embodiment.Then Mixing drum is transmitted to cast region, by geo-polymer slurry cast on concrete slab.Repetition mixed as described above Journey 13 times, whole concrete slab cast region is covered to obtain enough slurries.Geo-polymer slurry very easily flows With flatten.Use the material in even mud chi further promotion and mobile cast region.

Then the surface of mould material is smeared using steel trowel, to produce flat smooth surface.Depending on the position of plate, The effective thickness of mould material is about 1 inch to featheredge (about 1/16 inch).When material is cast on plate in measurement plate Mould material effective thickness, then measure the effective thickness again after about 2 hours.Thickness measure cast when and Keep substantially the same after about 2 hours.The total length for pouring into a mould the featheredge material in region is about 22 feet.It is worth noting that Mould material easily skiving side.It was found that being bonded in about 2 hours of cast between featheredge material and base material is excellent.It is worth It is noted that when pulling masking tape in the end in featheredge region when when about 2 is small, cracking or layer does not occur at featheredge From.After cast in about 2 hours, plate surface is dry and machinable.Floor remains substantially without crackle and defect, until When the last inspection carried out after the several months after cast.

According to ASTM F710-11 method of testings at the top of each time interval measurement geo-polymer binding agent floor table The surface p H in face.Surface p H measurements are carried out using EXTECH PH150-C EXSTICK concrete pH meter.Table 88 shows floor Top surface measures pH value：

The geo-polymer binding agent of the dimensionally stable of the embodiment due to their relatively low pH and can with it is most of Commercially available floor commercial organic binder (such as acrylic compounds and rubber adhesive) highly compatible.Due to the dimensionally stable by the embodiment The low ph conditions that geo-polymer binding agent is provided, adhesive for floor coverings do not show significantly due to geopolymer formulation Adverse effect caused by chemical breakdown and unstability.As a result, such as vinyl foils, vinyl ceramic tile (VCT) and The flooring material of carpet can successfully be installed on the geo-polymer binding agent of the dimensionally stable of the embodiment, with ensure persistently and Durable performance.

According to ASTM C1583 (2004) the method for testings geo-polymer top material that measurement was applied at six weeks to mixed The tensile bond strength of solidifying soil matrix material.Measure tensile strength values and be more than about 300psi, illustrate to generate material at the top of geo-polymer Expect the good adhesion to concrete substrate.

When as repairing or during Self-leveling top material, the geo-polymer of the dimensionally stable of some embodiments of the present invention The minimum base material preprocessing for being used for successfully installation of composition requirement.Depending on application, may be such that to make surface prepare to be used for The base material preprocessing method being time-consuming and expensive of Self-leveling geo-polymer binding agent top material is installed (such as on existing base material Shot-peening, cut, spray water, scabble or milling) it is minimized or avoid completely.Geo-polymer top material can be directly cast in not On base material containing dust and chip, or, it can be cast on the base material suitably primed using suitable ground electroplate primer.

Cementitious composition can be spread on substrate surface, wherein being glued binding agent for Self-leveling, and be poured into about 0.02 to about 7.5cm effective thickness.During repairing repair materials or Self-leveling top material on as existing base material, this hair The geopolymer formulation of the dimensionally stable of some bright embodiments can easily be applied to minimum thickness (by skimming face Layer is to featheredge).Skimming surface and featheredge are herein referring to be less than about 1/4 inch (0.635cm), more preferably from about 1/8 inch to about 1/ 128 inches (0.32cm's to 0.02cm) applies material thickness.

The geopolymer formulation of the dimensionally stable of some currently preferred embodiments of the present invention can produce with lower substrate Excellent tensile bond strength.Preferred tensile bond strength between the geology polymer material and concrete substrate of the present invention is excellent Choosing is more than about 200psi (1.4MPa), most preferably more than about 300psi (2.1MPa).

Important unique aspect such as the geo-polymer adhesive composition of the invention protruded by the example is as follows：

To obtain the extremely low mixed tensor requirement of the geo-polymer binder material well mixed, even with Low RPM rigs blender.It is especially noted that although using minimal amount of water in formula, the geology of the embodiment is gathered Compound material also easily mixes.Available generally available splicing is formulated using the water of about doubling dose to promote mixing simultaneously in industry Produce machinable Self-leveling slurry mix.

Using the geo-polymer binding agent top material of the embodiment, it is necessary to which minimum base material preprocessing succeeds Cast.Without using be time-consuming and expensive base material preprocessing method (such as shot-peening, cut, spray water, scabble or milling) so that surface Prepare to be used to pour into a mould.Geology polymer material can be directly cast on the base material without dust and chip, or, it can be poured Note on the base material suitably primed using suitable ground electroplate primer.

The geo-polymer binder material of the embodiment can be by skiving side.

Excellent bonding between the geo-polymer binding agent top material and concrete substrate of the embodiment.

The geo-polymer binding agent top material of the embodiment can process after cast in about 2 hours.

High resistance of the geo-polymer binding agent top material of the embodiment to damage (such as leafing and cracking).

The geo-polymer binder material of the embodiment can be poured into different thickness.

Geo-polymer binder material can receive different types of coating on the surface.

Geo-polymer binding agent top material can use commercially available continuous slurry blender and other kinds of concrete Mortar batch mixer mixes.

Example 27

Table 89 shows the raw material composition for the splicing mixture studied in the example.

The amount of calcium sulphoaluminate cement used is equal to the 25wt% of flying dust weight in the blend composition of the example.This grinds (it is C class to particulate calcium sulfate dihydrate (particulate land plaster) used using the 50wt% of the weight of calcium sulphoaluminate cement in studying carefully The 12.5wt% of flying dust) horizontal addition.With the 25 of flying dust, 67,150 and 400wt% level, (it is respectively Portland cement 15wt%, 33wt%, 52wt% and 74wt% of total adhesive material substantially ratio) addition.Total adhesive material flies including C classes Ash, calcium sulfate dihydrate, calcium sulphoaluminate and Portland cement.For all mixtures studied, water/total adhesive material ratio It is held constant at about 0.3.Add the Sheng Mali of state of Michigan Detroit type III Portland cement (St.Mary ' s Type III Portland Cement, Detroit, MI).Also QUIKRETE commerical grade fine sands No.1961 and BASF are used CASTAMENT FS20 superplasticizers.

Initial flow behavior and slump

Table 90 shows that is studied in example 27 includes flying dust, calcium sulphoaluminate cement, land plaster, Portland cement and alkali gold Belong to initial flow behavior and the slump characteristic of the cementitious composition of citrate.

All blend compositions studied are respectively provided with poor flow behavior, are such as observed in the test that collapses hard Slurry and small cake diameter shown in.The flowing property of material reduces with the increase of Portland cement in composition.

Slump value in table 90, the hard high viscosity property of slump cake are also apparent.Slurry mix is with group The increase of Portland cement in compound and become more tacky.

Shrinkage behavior

Figure 24 shows the Shrinkage behavior of the geo-polymer cementitious composition for the embodiment studied in example 27.From by original Material mixes starts to shrink at measurement to be formed when water paste plays about 2-1/5 hours.Solidify under about 75 °F/50%RH While material, measurement Material shrinkage was of about the total duration of 8 weeks.

Following important conclusion can be drawn by the research and Figure 24：

Incorporation Portland cement significantly increases the contraction of studied cementitious composition.The each mixture studied Final shrinkage value is tabulated in table 91.It is observed that the final contraction of the mixture #1 containing about 15% Portland cement It is about 0.15%.For the mixture #2 of the Portland cement containing about 33%, final shrink increases to about 0.23%.For containing There is the mixture #3 of about 50% Portland cement, final shrink increases to about 0.3%.Finally, for the ripple with about 75% The mixture #4 of special blue cement, measures contraction highest, is about 0.5%.

It is discussed in detail as described above, the example is shown, Portland cement is added in embodiments of the invention and obtained The unexpected result obtained is that Portland cement has adverse effect to the Shrinkage behavior of composition.The example is shown, is shunk Magnitude with composition the amount of Portland cement increase and proportional increase.

Portland cement is added to this hair for including flying dust, calcium sulphoaluminate cement, calcium sulfate and alkali-metal citrate The cementitious composition pole of bright embodiment significantly increases Material shrinkage.

Based on above-mentioned discovery, do not recommend to add in the geopolymer formulation of the dimensionally stable of embodiments of the invention Portland cement.

Example 28

Table 92 shows the raw material composition of the splicing mixture in the example.

The amount of calcium sulphoaluminate cement used is equal to the 20wt% of flying dust weight in the blend composition of the example.This grinds Particulate calcium sulfate dihydrate (particulate land plaster) used is with 50wt% the and C class flying dusts of the weight of calcium sulphoaluminate cement in studying carefully 10wt% the horizontal addition of amount.The composition of mixture 1 not borax, and the composition of mixture 2 to 4 contains borax as solidification Control chemical addition agent.QUIKRETE commerical grade fine sand No.1961, BASF CASTAMENT FS20 superplasticizers, WACKER Vinnapas5025L (Wacker Polymer Company (Wacker Polymers)) and from Air Products Company (Air Products Surfynol500S defoamers).

Weathering behavior

Figure 25 shows the mixture for being studied in the example, the cubical photograph cast in brass cube mold Piece.Cast visible in cubical top surface photo shown in the figure.It is observed that mixture (the mixture # with borax 2nd, #3 and #4) show the excessive weathering on cube top surface caused by salt leaches out of material.Without borax Mixture #1 cube do not have weathering substantially.Excessive weathering can cause the aesthetic feeling of difference, occur due to the hydration of salt Expansion reaction caused by material damage and damage, and the reduction with other base materials and the adhesion strength of face coat.

The behavior of bonding

It is, it was also found that steady with the size according to the present invention as the borax of other component addition, borate or boric acid Fixed geo-polymer adhesive composition produces the poor bonding with other materials and base material (such as concrete).Therefore, originally The composition of invention does not preferably include borax, borate or boric acid.

Example 29：C classes flying dust adds low lime ca aluminosilicate mineral matter (F classes flying dust)

Table 93 shows that the geo-polymer studied in the example is glued the raw material composition of mixture.

The case study low lime ca aluminosilicate mineral matter of incorporation (comes from riverhead resource company (Headwaters Resources F classes flying dust)) and C classes flying dust to the present invention geopolymer formulation physical property influence.C classes Flying dust is added with 76,38,18 and 76 parts by weight, and F flying dusts are added with 38 and 58 parts by weight, in mixture 2 and 3, C class flying dusts Added respectively with the level of 38 and 18 parts by weight.Calcium sulfate dihydrate is added with 8 parts by weight, and calcium sulphoaluminate is with 16 parts by weight Level addition.Also add QUIKRETE commerical grades fine sand No.1961, BASF CASTAMENT FS20 superplasticizers and SURFYNOL500S defoamers.

The slump of material and flow behavior

Table 94 show the geo-polymer cementitious composition for the embodiment studied in example 29 initial flow behavior and Slump characteristic.

All blend compositions studied are respectively provided with good rheology and slump behavior, as seen in the test that collapses Observe.It is especially noted that under as little as about 0.24 water/adhesive material ratio, can also obtain this good Rheology and slump behavior.

Shrinkage behavior

Figure 26 shows the Shrinkage behavior of the geo-polymer cementitious composition for the embodiment studied in example 29.The research Main purpose be study incorporation with low lime content the aluminosilicate mineral material (F classes flying dust) through thermal activation to the reality Apply the influence of the Shrinkage behavior of the geo-polymer cementitious composition of the exploitation of example.

From raw material is mixed to start to shrink at measurement when about 4 hours forming water paste.About 75 °F/ Under 50%RH while curing materials, measurement Material shrinkage was of about the total duration of 8 weeks.

It can be drawn the following conclusions by the research and Figure 26：

(mixed when composition only contains the aluminosilicate mineral material (i.e. C classes flying dust) through thermal activation with high-lime Compound #1) when, Material shrinkage is minimum.

Material shrinkage with the increase of the amount of the aluminosilicate mineral material through thermal activation of low lime content in composition and Increase.About 0.04% is always punctured into the absence of the mixture 1 of the aluminosilicate mineral material through thermal activation of low lime content.Can It was observed that there is the total of the mixture 2 of the aluminosilicate mineral material through thermal activation of about 50% low lime content in composition Contraction increases to about 0.07%.There is the aluminosilicate mineral material through thermal activation of about 76% low lime content in composition Total Material shrinkage of mixture 3 increases to about 0.1%.With about 100% low lime content through thermal activation in composition Total Material shrinkage of the mixture 4 of aluminosilicate mineral material is considerably higher, is about 0.18%.

Setting time

Table 95 shows the setting time of the geo-polymer cementitious composition of the embodiment in example 29.

It was observed that the initial and final setting time for the composition studied in the example is with low lime content in formula The aluminosilicate mineral material through thermal activation amount increase and increase.It can be observed, contain about 100% low lime content The final setting time of the mixture 4 of aluminosilicate mineral material through thermal activation is increased significantly to be more than about 2 hours.

Compressive strength

Table 96 shows the compressive strength row of the geo-polymer cementitious composition of the exploitation of the embodiment in example 29 For.

By the research, following observation can be drawn：

The geology of the mixture of the aluminosilicate mineral material through thermal activation comprising high-lime and low lime content is gathered The compressive strength of compound cementitious composition continues to increase with the time.

The early stage compressive strength and final compressive strength of blend composition are with the silicon of low lime content in composition The increase of the amount of aluminium mineral material matter and reduce.

The early stage compressive strength of the mixture 2 of aluminosilicate mineral material containing about 50% low lime content in composition It is gratifying with final compressive strength, its 28 days compressive strengths are more than about 4200psi.

In composition containing about 100% low lime aluminosilicate mineral material mixture 4 early stage compressive strength and Final compressive strength is relatively low, and is unsatisfactory for many applications desired by the part as the present invention.

Example 30

The example shows, geo-polymer cementitious composition of the invention particularly useful as multiple base materials (such as concrete, Timber etc.) on Self-leveling floor lining.Especially, the composition similar with the composition being described in the example is particularly useful for Make the existing concrete smooth surface of coarse non-flat forms and flatten.

Table 97 shows the material compositions of the embodiment.

The blend composition studied in the example has good rheology, and produces 10-1/4 English in the test that collapses The slump of very little (26cm).The slump cake of the blend composition keeps excellent state after drying, and does not produce any split Line.

Shrinkage behavior

Figure 27 A show the contraction row of the geo-polymer cementitious composition for the embodiments of the invention studied in example 29 For.

From raw material is mixed to start to shrink at measurement when about 4 hours forming water paste.About 75 °F/ Under 50%RH while curing materials, measurement Material shrinkage was of about the total duration of 8 weeks.

Following important conclusion can be drawn by the research and Figure 27 A：

With even before the demoulding comparative example 4 (not having calcium sulfate) of cracking contraction rod on the contrary, including calcium sulfate two The contraction rod complete stability of the example 29 of hydrate, and do not produce any crackle before or after the demoulding.

Compared to about 0.75% of control mixture composition (example 1) only containing flying dust and alkali-metal citrate Maximum collapse, that studies in this example includes flying dust, calcium sulphoaluminate cement, calcium sulfate dihydrate and alkali-metal citrate Embodiments of the invention geo-polymer cementitious composition have only about 0.04% maximum collapse.

Heat release and slurry temperature rise behavior

Figure 27 B show the geo-polymer cementitious composition for the embodiments of the invention studied in example 29 heat release and Slurry temperature rise behavior.The cementitious composition shows only extremely gentle temperature rise behavior, and maximum slurry temperature only reaches 108 °F.

Gentle heat release in cure stage process in which materials and low-temperature-rise assist to prevent the excessive thermal expansion of material and with Cracking and destruction afterwards.When material by wherein actual field application in be related to big thickness material cast in a manner of in use, institute Stating aspect becomes even more helpful.The geo-polymer cementitious composition of the embodiment of the present invention is in the particular aspects Highly advantageous, because the resistance to thermal cracking that they will produce lower thermal expansion and improve in applying at the scene.

Setting time

Table 98 shows the solidifying of the geo-polymer cementitious composition for some embodiments of the present invention studied in example 29 Gu the time.These acetonideexamples of the present invention, also it is particularly useful in the application of Self-leveling end liner.

Compressive strength

Table 99 shows the geo-polymer cementitious composition of the exploitation for the embodiments of the invention studied in the example Compressive strength behavior.These results show that the geopolymer formulation of the present invention is used in the application of Self-leveling end liner be adapted to Property.

Example 31

It this example illustrate unique row of the lightweight geo-polymer adhesive composition of some embodiments of the present invention For and mechanical performance.

Table 100 shows that the lightweight geo-polymer studied in the example is glued the raw material composition of mixture.

The lightweight geopolymer formulation studied in the example to measure density as follows：

Mixture #1：96pcf (pound/cubic feet)

Mixture #2：101pcf

Mixture #3：105pcf

The slump and early stage cracking behavior of material

Table 101 shows the lightweight geo-polymer cementitious composition for some embodiments of the present invention studied in the example Slump behavior.

All blend compositions studied are respectively provided with good rheology and slump behavior, as seen in the test that collapses Observe.It is especially noted that under as little as about 0.255 water/adhesive material ratio, can also obtain this good Rheology and slump behavior.

All slump cakes for the mixture studied in the example do not produce any cracking under excellent condition.

Heat release and slurry temperature rise behavior

Figure 28 A show the lightweight geo-polymer cementitious composition for some embodiments of the present invention studied in example 31 Heat release and slurry temperature rise behavior.It is observed that these compositions show extremely low temperature rise behavior.In cure stage process Gentle heat release and low-temperature-rise in middle material prevent that the excessive thermal expansion of material and subsequent cracking and destruction from being aobvious for assistance Write.When material by wherein actual field application in be related to big thickness material cast in a manner of in use, the aspect becomes It is even more helpful.The geo-polymer cementitious composition for some embodiments of the present invention studied in the example is disclosed as in institute It is highly advantageous to state particular aspects, because they will produce lower thermal expansion and improve to heat in actual field application The resistance of cracking.

Setting time

Table 102 shows the solidifying of the lightweight geo-polymer cementitious composition for the embodiments of the invention studied in the example Gu the time.It is observed that all cementitious compositions studied in the example show final setting time for 1 to 2 hour it Between quick solidification behavior.

Compressive strength

Table 103 shows the pressure of the lightweight geo-polymer cementitious composition for the embodiments of the invention studied in example 31 Contracting intensity behavior.

By the research, following observation can be drawn：

The early stage compressive strength and final compressive strength of the lightweight geopolymer formulation of the present invention are relatively high, and With in the theoretical density composition of the present invention some are comparable (compared with result and those results of example 31 from example 30).

It is worth noting that 4 hours compressive strengths of the lightweight geopolymer formulation of the invention studied in the example More than about 1000psi.

Also it is worth noting that 24 hours compressive strengths of the lightweight geopolymer formulation of the present invention are more than about 2500psi。

Again highly it is to be noted that 28 days compressive strength poles of the lightweight geo-polymer cementitious composition of the present invention Height, i.e., more than about 4000psi.

The geopolymer formulation of some currently preferred embodiments of the present invention shown in example is in multiple commercial products With application.Especially, composition can be used for：

Repair the roads and road repair product, traffic load-bearing surface and road surface, one as disclosed in example 5,24,25,30 and 31 Shown in a little properties；

Brick and compound stone, shown in the properties as disclosed in example 5,6,9,12 and 14；

The patching material of wall, floor and ceiling and adhesive mortar, gypsum and panel surface material, such as example 5,24 and 33 Disclosed in properties shown in；

Roof Material, shown in the properties as disclosed in example 5,26,30 and 31；

As the injection cementitious product for soil and Rock Mass Stability and the gunite concrete product as gasket material, Shown in properties as disclosed in example 5,25 and 30；

Load-carrying members, shown in the properties as disclosed in example 25,30 and 31；

Sculpture and building mechanograph, shown in the properties as disclosed in example 5-22,29,30 and 31；

Self-leveling end liner, the properties institute as disclosed in example 5,7,9,13,15,19,21,22,24,26,30 and 31 Show.

Notwithstanding implementation the preferred embodiments of the present invention, but the disclosure is not it will be appreciated by a person skilled in the art that In the case of deviateing the scope of the present invention, the present invention can be modified and be added.

Claims (28)

1. a kind of alumino-silicate geopolymer formulation, it includes following reaction product：

Water；

Chemical activating agent selected from alkali metal salt, alkali metal base and their mixture；With

Cementation reaction material, wherein the cementation reaction material includes：

Aluminosilicate mineral material through thermal activation；

Calcium sulphoaluminate cement；With

Calcium sulfate selected from calcium sulfate dihydrate, calcium sulfate hemihydrate, dead plaster and their mixture, and

Without Portland cement,

The weight ratio of wherein described chemical activating agent and the cementation reaction material is 1 to 6:100；And

Wherein described cementation reaction material includes：

33 to the 97 weight % aluminosilicate mineral material through thermal activation,

1 to 40 weight % calcium sulphoaluminate cement,

1 to 40 weight % calcium sulfate.

2. composition according to claim 1,

The weight ratio of wherein described chemical activating agent and the cementation reaction material is 1 to 6:100；

The weight ratio of wherein described water and the cementation reaction material is 0.17 to 0.40:1；

The weight ratio of wherein described calcium sulphoaluminate cement and the aluminosilicate mineral material through thermal activation is 2 to 100:100；And

The weight ratio of wherein described calcium sulfate and the calcium sulphoaluminate cement is 2 to 100:100.

3. composition according to claim 1, wherein the chemical activating agent includes alkali-metal citrate, and the warp The aluminosilicate mineral material of thermal activation includes C class flying dusts.

4. composition according to claim 1, wherein the chemical activating agent and calcium sulfate have relative to described through heat The aluminosilicate mineral material of activation and the amount of calcium sulphoaluminate cement, the amount is effective so that reaction product with water after mixing With the final setting time of 30 to 120 minutes.

5. composition according to claim 1,

Wherein relative to the aluminosilicate mineral material through thermal activation and the chemical activating agent and sulphur of the amount of calcium sulphoaluminate cement The amount of sour calcium is effective so that reaction product has final solidification after being mixed with water in 45 minutes to 130 minutes；

Wherein described cementation reaction material contains calcium sulfate dihydrate；

The weight ratio of wherein described calcium sulfate dihydrate and calcium sulphoaluminate cement is 20 to 60:100；

Wherein described cementation reaction material and chemical activating agent include alkali-metal citrate, wherein the alkali metal citric acid The weight ratio of salt and the cementation reaction material is 2 to 3:100；And

Wherein described calcium sulfate dihydrate has 1 to 30 micron of particle mean size.

6. composition according to claim 1,

Wherein described calcium sulfate has the particle mean size in 1 to 100 micrometer range,

Wherein described cementation reaction material contains dead plaster,

The weight ratio of wherein described dead plaster and the calcium sulphoaluminate cement is 10 to 60:100；And

Wherein described composition has the final setting time of 30 to 60 minutes.

7. composition according to claim 1, wherein the sulphur aluminium of the amount relative to the aluminosilicate mineral material through thermal activation The amount of sour calcium cement, calcium sulfate and chemical activating agent is effective so that the contraction of the composition is limited to less than 0.3%.

8. composition according to claim 1, wherein the cementation reaction material includes：

60 weight % to the 90 weight % aluminosilicate mineral material through thermal activation, wherein the aluminosilicate mineral through thermal activation Material includes C class flying dusts；

4 weight % to 35 weight % calcium sulphoaluminate cement,

2 weight % to 15 weight % calcium sulfate, and

The weight ratio of wherein described chemical activating agent and the cementation reaction material is 1.25 to 4:100.

9. composition according to claim 1, wherein the reaction product derives from the exothermic reaction in water slurry, wherein Amount relative to the calcium sulphoaluminate cement of the amount of the aluminosilicate mineral material through thermal activation, calcium sulfate and chemical activating agent is effective So that maximum slurry temperature rise is limited to 50 °F.

10. composition according to claim 1, wherein the composition have be enough collapse test in produce it is a diameter of 9 to 11 inches of slump cake and mobility and machinability without cracking when drying.

11. the composition according to claim 1 or 10, wherein the reaction product has：

500psi (3.5MPa) to 4000psi (28MPa) 4 hours compressive strengths；

1500psi (10MPa) to 5000psi (34.5MPa) 24 hours compressive strengths；

3500psi (24MPa) to 10000psi (70MPa) 28 days compressive strengths；With

The final setting time of 10 minutes to 240 minutes.

12. composition according to claim 1, it is the form of building repairing material.

13. composition according to claim 1, it is the form of floor patching material.

14. composition according to claim 1, its form served as a contrast for the Self-leveling floor on base material.

15. composition according to claim 1, it is the form of bearing structure.

16. composition according to claim 1, it is the form of panel surface material.

17. composition according to claim 1, it is the form of the binding agent in construction material.

18. composition according to claim 1, it is the form of the construction material selected from brick, block and stone.

19. composition according to claim 1, it is the form of wall surface material.

20. composition according to claim 1, it is the form of the ground surface material for traffic load-bearing surface.

21. composition according to claim 1, it is the form of the patching material for traffic load-bearing surface.

22. composition according to claim 1, it is the form of the material for load-carrying members.

23. composition according to claim 1, it is the form of roof Material.

24. composition according to claim 1, it is the form of gunite concrete material.

25. composition according to claim 1, it is the form of mortar.

26. a kind of method for preparing the alumino-silicate geopolymer formulation any one of claim 1-25, it is wrapped Including reacts the mixture of following component：

Water；

Chemical activating agent selected from alkali metal salt, alkali metal base and their mixture；With

Cementation reaction material, wherein the cementation reaction material includes：

Aluminosilicate mineral material through thermal activation,

Calcium sulphoaluminate cement, and

Calcium sulfate selected from calcium sulfate dihydrate, calcium sulfate hemihydrate, dead plaster and their mixture.

27. a kind of mixture for being used to form alumino-silicate geopolymer formulation, it is included：

Aluminosilicate mineral material through thermal activation；The wherein described aluminosilicate mineral material through thermal activation includes C class flying dusts,

Calcium sulphoaluminate cement,

Calcium sulfate selected from calcium sulfate dihydrate, calcium sulfate hemihydrate, dead plaster and their mixture；With selected from The chemical activating agent of alkali metal salt, alkali metal base and their mixture；With

Without Portland cement,

The weight ratio of wherein described calcium sulphoaluminate cement and the aluminosilicate mineral material through thermal activation is 1 to 100:100；And

The weight ratio of wherein described calcium sulfate and the calcium sulphoaluminate cement is 2 to 100:100.

28. a kind of cementation reaction material for being used to form alumino-silicate geopolymer formulation, it is included：

60 weight % to the 85 weight % mineral matter through thermal activation, wherein the mineral matter through thermal activation includes C class flying dusts,

8 weight % to 30 weight % calcium sulphoaluminate cement, and

4.0 weight % to 15 weight % selected from calcium sulfate dihydrate, calcium sulfate hemihydrate, dead plaster and they The calcium sulfate of mixture, and

Chemical activating agent selected from alkali metal salt, alkali metal base and their mixture, and

Without Portland cement.